Abstract:

A method of producing value-added product from refinery-related gas, the
method comprising: providing a refinery-related gas comprising at least
one selected from C1-C8 compounds; intimately mixing the refinery-related
gas with a liquid carrier in a high shear device to form a dispersion of
gas in the liquid carrier, wherein the gas bubbles in the dispersion have
a mean diameter of less than or equal to about 5 μm; and extracting
value-added product comprising at least one component selected from
higher hydrocarbons, olefins and alcohols. A system for producing
value-added product from refinery-related gas comprising: at least one
high shear device comprising at least one rotor and at least one
complementarily-shaped stator; apparatus for the production of a
refinery-related gas comprising one or more of C1-C8 compounds; and a
pump configured for delivering a liquid stream comprising the liquid
carrier to the high shear device.

Claims:

1. A method of producing value-added product from refinery-related gas,
the method comprising:(a) providing a refinery-related gas comprising at
least one compound selected from the group consisting of C1-C8 compounds
and combinations thereof;(b) intimately mixing the refinery-related gas
with a liquid carrier in a high shear device to form a dispersion of gas
in the liquid carrier, wherein the gas bubbles in the dispersion have a
mean diameter of less than or equal to about 5 micron(s); and(c)
extracting value-added product comprising at least one component selected
from the group consisting of higher hydrocarbons, olefins, alcohols,
aldehydes, and ketones.

12. A method of increasing the API gravity of a crude oil, the method
comprising:introducing the crude oil and a gas selected from the group
consisting of oxygenates, associated gas, unassociated gas, light gas
from claim 10, and combinations thereof into a high shear device
comprising at least one rotor and at least one stator; androtating the
rotor to provide a tip speed of at least 22.9 m/s.

13. The method of claim 12 wherein the API gravity is increased by a
factor of at least 1.5.

14. A system for producing value-added product from refinery-related gas,
the system comprising:at least one high shear device comprising at least
one rotor and at least one complementarily-shaped stator, configured to
produce a dispersion comprising bubbles of refinery-related gas in a
liquid carrier;apparatus for the production of a refinery-related gas
comprising one or more of C1-C8 compounds; anda pump configured for
delivering a liquid stream comprising the liquid carrier to the high
shear device.

15. The system of claim 14 further comprising a vessel coupled to said
high shear device, said vessel configured for receiving the dispersion
from said high shear device.

16. The system of claim 14 wherein the at least one rotor is rotatable at
a tip speed of at least 22.9 m/s (4,500 ft/min), wherein the tip speed is
defined as πDn, where D is the diameter of the rotor and n is the
frequency of revolution.

17. The system of claim 14 wherein the at least one rotor is separated
from the at least one stator by a shear gap in the range of from in the
range of from about 0.02 mm to about 5 mm, wherein the shear gap is the
minimum distance between the at least one rotor and the at least one
stator.

18. The system of claim 14 wherein the at least one rotor is able to
provide shear rate of at least 20,000 s-1 during operation, wherein
the shear rate is defined as the tip speed divided by the shear gap, and
wherein the tip speed is defined as πDn, where D is the diameter of
the rotor and n is the frequency of revolution.

19. The system of claim 14 comprising more than one high shear device.

20. The system of claim 14 wherein the high shear device comprises at
least two generators, wherein each generator comprises a rotor and a
complementarily-shaped stator.

21. The system of claim 14 wherein apparatus for the production of
refinery-related gas comprises a cracker configured for breaking organic
molecules into simpler molecules.

22. The system of claim 14 wherein the apparatus for the production of
refinery-related gas comprises an oil refinery or some components
thereof, a fossil fuel burning facility or some components thereof.

23. The system of claim 22 wherein the fossil fuel burning facility is a
power plant or a power station.

Description:

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001]This application claims the benefit under 35 U.S.C. §119(e) of
U.S. Provisional Patent Application No. 61/229,082, filed Jul. 28, 2009,
the disclosure of which is hereby incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002]Not Applicable.

BACKGROUND

[0003]1. Technical Field

[0004]The present invention relates generally to production of value-added
products from refinery-related gas. More particularly, the present
invention relates to an apparatus and process for producing product
comprising oxygenate(s) via shear-promoted reaction of refinery-related
gas.

[0007]Many of the processes utilized in oil refineries create large
quantities of gas. A substantial quantity of this gas is negative-value
gas, i.e. there is financial loss incurred in disposing of the gas. Much
of the gas produced in a refinery is sent to a gas plant which serves to
create value-added products or otherwise treat the gas before its use as
a fuel gas or flaring of the gas to the environment. Flaring may be
undesirable due to environmental regulations. Additionally, crude oil is
often discovered with associated gas which is generally separated
therefrom prior to refining of the crude oil.

[0008]Accordingly, there is a need in industry for systems and processes
of converting refinery-related gas into value-added products. Desirably,
the conversion is such that the conversion of the refinery-related gas to
value-added product is economically beneficial. Desirably, the system and
process may be incorporated into existing refineries or designed into the
building of new refineries. There is also a need for systems and
processes for enhancing the API of crude oil and/or increasing the
stability of crude oil. Elimination of catalyst entirely is also possible
in some instances.

SUMMARY

[0009]Herein disclosed is a method of producing value-added product from
refinery-related gas, the method comprising: providing a refinery-related
gas comprising at least one compound selected from the group consisting
of C1-C8 compounds and combinations thereof; (b) intimately mixing the
refinery-related gas with a liquid carrier in a high shear device to form
a dispersion of gas in the liquid carrier, wherein the gas bubbles in the
dispersion have a mean diameter of less than or equal to about 5
micron(s); and (c) extracting value-added product comprising at least one
component selected from the group consisting of higher hydrocarbons,
olefins, alcohols, aldehydes, and ketones. In some cases, the
refinery-related gas is selected from the group consisting of pyrolysis
gas, FCC offgas, associated gas, hydrodesulfurization offgas, coker
offgas, catalytic cracker offgas, thermal cracker offgas, and
combinations thereof. In some cases, the C1-C8 compounds comprise carbon
dioxide.

[0010]In an embodiment, alcohol as the value-added product is selected
from the group consisting of methanol, ethanol, isopropanol, butanol, and
propanol. In an embodiment, step (b) further comprises contacting the
refinery-related gas and the carrier with a catalyst. In some cases, the
catalyst comprises at least one component selected from the group
consisting of phosphoric acid, sulfonic acid, sulfuric acid, zeolites,
solid acid catalysts, and liquid acid catalysts. In some embodiments, the
carrier is a catalyst. In some embodiments, the carrier comprises
sulfuric acid. In some embodiments, the carrier comprises water. In an
embodiment, step (c) comprises separating a light gas from the carrier
and the value-added product. In another embodiment, the method further
comprises contacting the carrier and the refinery-related gas with a
catalyst selected from the group consisting of hydrogenation catalysts,
hydroxylation catalysts, partial oxidation catalysts,
hydrodesulfurization catalysts, hydrodenitrogenation catalysts,
hydrofinishing catalysts, reforming catalysts, hydration catalysts,
hydrocracking catalysts, Fischer-Tropsch catalysts, dehydrogenation
catalysts, and polymerization catalysts.

[0011]In an embodiment, a method of increasing the API gravity of a crude
oil is described. The method comprises: introducing a crude oil and a gas
selected from the group consisting of oxygenates, associated gas,
unassociated gas, light gas separated from the carrier and the
value-added product, and combinations thereof into a high shear device
comprising at least one rotor and at least one stator; and rotating the
rotor to provide a tip speed of at least 22.9 m/s. In some embodiments,
the API gravity is increased by a factor of at least 1.5.

[0012]Further described in this disclosure is a system for producing
value-added product from refinery-related gas, the system comprising: at
least one high shear device comprising at least one rotor and at least
one complementarily-shaped stator, configured to produce a dispersion
comprising bubbles of refinery-related gas in a liquid carrier; apparatus
for the production of a refinery-related gas comprising one or more of
C1-C8 compounds; and a pump configured for delivering a liquid stream
comprising the liquid carrier to the high shear device. In some
embodiments, the system further comprises a vessel coupled to the high
shear device, the vessel configured for receiving the dispersion from the
high shear device.

[0013]In an embodiment, the at least one rotor is rotatable at a tip speed
of at least 22.9 m/s (4,500 ft/min), wherein the tip speed is defined as
πDn, where D is the diameter of the rotor and n is the frequency of
revolution. In an embodiment, the at least one rotor is separated from
the at least one stator by a shear gap in the range of from in the range
of from about 0.02 mm to about 5 mm, wherein the shear gap is the minimum
distance between the at least one rotor and the at least one stator. In
an embodiment, the at least one rotor is able to provide shear rate of at
least 20,000 s-1 during operation, wherein the shear rate is defined
as the tip speed divided by the shear gap, and wherein the tip speed is
defined as πDn, where D is the diameter of the rotor and n is the
frequency of revolution.

[0014]In an embodiment, the system comprises more than one high shear
device. In an embodiment, the high shear device comprises at least two
generators, wherein each generator comprises a rotor and a
complementarily-shaped stator. In an embodiment, the apparatus for the
production of refinery-related gas comprises a cracker configured for
breaking organic molecules into simpler molecules. In an embodiment, the
apparatus for the production of refinery-related gas comprises an oil
refinery or some components thereof, a fossil fuel burning facility or
some components thereof. In an embodiment, the fossil fuel burning
facility is a power plant or a power station.

[0015]Herein disclosed is a method of producing value-added product from
refinery-related gas, the method comprising: (a) providing a
refinery-related gas comprising at least one selected from primarily
C1-C8 compounds and hydrogen; (b) intimately mixing the refinery-related
gas with a liquid carrier in a high shear device to form a dispersion of
gas in the liquid carrier, wherein the gas bubbles in the dispersion have
a mean diameter of less than or equal to about 5 micron(s); and (c)
extracting value-added product comprising at least one component selected
from higher hydrocarbons, olefins and alcohols. In embodiments, the gas
bubbles have an average diameter of no more than about 5, 4, 3, 2, 1,
0.5, 0.4, 0.3, 0.2, or 0.1 μm. In embodiments, the gas bubbles have an
average diameter of no more than about 100 nm. The refinery-related gas
can be selected from pyrolysis gas, FCC offgas, associated gas,
hydrodesulfurization offgas, coker offgas, catalytic cracker offgas,
thermal cracker offgas, or other hydrocarbon processing or combustion
sources and combinations thereof. In embodiments, the high shear device
comprises at least one rotor and at least one stator and (b) comprises
subjecting the gas-liquid stream to high shear mixing at a tip speed of
at least about 23 msec, wherein the tip speed is defined as πDn, where
D is the diameter of the at least one rotor and n is the frequency of
revolution. In embodiments, the high shear device comprises at least one
rotor and at least one stator, and (b) comprises providing a shear rate
of at least 20,000 s-1, wherein the shear rate is defined as the tip
speed divided by the shear gap, and wherein the tip speed is defined as
πDn, where D is the diameter of the at least one rotor and n is the
frequency of revolution. Providing a shear rate of at least 20,000
s-1 may produce a local pressure of at least about 1034.2 MPa
(150,000 psi) at a tip of the at least one rotor. Providing a shear rate
of at least 20,000 s-1 may comprise rotating the at least one rotor
at a tip speed of at least 22.9 m/s (4,500 ft/min), wherein the tip speed
is defined as πDn, where D is the diameter of the rotor and n is the
frequency of revolution. Forming the dispersion can comprise an energy
expenditure of at least about 1000 W/m3, 5000 W/m3, 7500
W/m3, 1 kW/m3, 500 kW/m3, 1000 kW/m3, 5000
kW/m3, 7500 kW/m3, or greater.

[0016]In embodiments, (b) further comprises contacting the
refinery-related gas and the carrier with a catalyst. The catalyst may be
selected from solid acid catalysts and liquid catalysts. The catalyst may
be selected from phosphoric acid, sulfonic acid, sulfuric acid, zeolites,
hydrosilane and combinations thereof. Catalyst may also contain a noble
metal such as nickel, ruthenium, rhodium, or platinum as an active
component. Biocatalysts may also be utilized. In embodiments, the carrier
is a catalyst. In embodiments, the carrier comprises sulfuric acid. In
embodiments, the alcohol(s) produced comprises at least one selected from
methanol, ethanol, isopropanol, butanol, and propanol.

[0017]In embodiments, (c) comprises separating a light gas from the
carrier and the value-added product. The method may further comprise
subjecting the light gas to high shear. Subjecting the light gas to high
shear may comprise introducing the light gas into a high shear device
comprising at least one rotor and at least one stator in the presence of
a Fischer-Tropsch catalyst, whereby Fischer-Tropsch hydrocarbons are
produced. Subjecting the light gas to high shear may comprise providing a
shear rate of at least 20,000 s-1, wherein the shear rate is defined
as the tip speed divided by the shear gap, and wherein the tip speed is
defined as πDn, where D is the diameter of the at least one rotor and
n is the frequency of revolution. Subjecting the light gas to high shear
may comprise introducing the light gas and crude oil into a high shear
device comprising at least one rotor and at least one stator, and
subjecting the contents of the high shear device to a shear rate of at
least 20,000 s-1. In various embodiments, high shear is applied to
the light gas together with a liquid or slurry.

[0019]Also disclosed is a method of increasing the API gravity of a crude
oil, the method comprising: introducing the crude oil and a gas selected
from oxygenates, associated gas, unassociated gas, light gas from the
above-disclosed method of producing value-added product from
refinery-related gas, or a combination thereof into a high shear device
comprising at least one rotor and at least one stator; and rotating the
rotor to provide a tip speed of at least 22.9 m/s. In embodiments, the
API gravity is increased by a factor of at least 1.5. In embodiments, the
API gravity is increased by a factor of at least 2.

[0020]Also disclosed is a system for producing value-added product from
refinery-related gas, the system comprising: at least one high shear
device comprising at least one rotor and at least one
complementarily-shaped stator, configured to produce a dispersion
comprising bubbles of refinery-related gas in a liquid carrier; apparatus
for the production of a refinery-related gas comprising one or more of
C1-C8 compounds and hydrogen; and a pump configured for delivering a
liquid stream comprising the liquid carrier to the high shear device. The
system may further comprise a vessel coupled to the high shear device,
the vessel configured for receiving the dispersion from the high shear
device. In embodiments, the at least one rotor is rotatable at a tip
speed of at least 22.9 m/s (4,500 ft/min), wherein the tip speed is
defined as πDn, where D is the diameter of the rotor and n is the
frequency of revolution. In embodiments, the high shear device is
configured for operating at a tip speed of at least 40 msec. In
embodiments, the at least one rotor is separated from the at least one
stator by a shear gap in the range of from about 0.02 mm to about 5 mm,
wherein the shear gap is the minimum distance between the at least one
rotor and the at least one stator. In embodiments, the shear rate
provided by rotation of the at least one rotor during operation is at
least 20,000 s-1, wherein the shear rate is defined as the tip speed
divided by the shear gap, and wherein the tip speed is defined as πDn,
where D is the diameter of the rotor and n is the frequency of
revolution. In embodiments, the high shear device comprises two or more
rotors and two or more stators. In embodiments, the at least one high
shear device is configured for producing a dispersion of bubbles of
refinery-related gas in the liquid phase, wherein the dispersion has a
mean bubble diameter of less than about 5, 4, 3, 2, 1, 0.5, 0.4, 0.3,
0.2, or 0.1 μm. The system can comprise more than one high shear
device. In embodiments, the high shear device comprises at least two
generators, wherein each generator comprises a rotor and a
complementarily-shaped stator. The shear rate provided by one generator
may be greater than the shear rate provided by another generator.

[0021]In embodiments, the apparatus for the production of refinery-related
gas comprises a cracker configured for breaking organic molecules into
simpler molecules. The cracker may comprise a fluid catalytic cracker.
The cracker may comprise a thermal cracker. The thermal cracker may
comprise a coker. In embodiments, the apparatus for the production of
refinery-related gas comprises a steam cracker. In embodiments, the
apparatus for the production of refinery-related gas comprises an oil
refinery or some components thereof.

[0022]Also disclosed is a system for producing value-added product from
FCC offgas, the system comprising: at least one high shear device
comprising at least one rotor and at least one complementarily-shaped
stator, wherein the at least one rotor is rotatable at a tip speed of at
least 22.9 m/s (4,500 ft/min), wherein the tip speed is defined as
πDn, where D is the diameter of the rotor and n is the frequency of
revolution; fluid catalytic cracking apparatus configured for the
catalytic cracking of a FCC feedstock and operable to produce a FCC
offgas, the at least one high shear device in fluid communication with a
line configured for carrying at least a portion of the FCC offgas to the
at least one high shear device; and a pump configured for delivering a
liquid stream comprising liquid carrier to the high shear device. In
embodiments, the FCC feedstock comprises AGO, VGO, light vacuum
distillate, heavy vacuum distillate, or a combination thereof. The system
may further comprise a fluid catalytic cracking vapor recovery unit
configured for separating at least one component from the FCC offgas. In
embodiments, the high shear device is operable to produce a dispersion of
the FCC offgas in the liquid carrier, wherein the bubbles of FCC offgas
in the dispersion have an average bubble diameter of less than 5 microns.
In embodiments, the bubbles of FCC offgas in the dispersion have a bubble
diameter of less than 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1 μm. In
embodiments, the at least one rotor is rotatable at a tip speed of at
least 40 m/s.

[0023]Also disclosed is a system for producing value-added product from
coker offgas, the system comprising: at least one high shear device
comprising at least one rotor and at least one complementarily-shaped
stator, wherein the at least one rotor is rotatable at a tip speed of at
least 22.9 m/s (4,500 ft/min), wherein the tip speed is defined as
πDn, where D is the diameter of the rotor and n is the frequency of
revolution; a coker configured for thermal cracking of a coker feedstock
and operable to produce a coker offgas, the at least one high shear
device in fluid communication with a line configured for carrying at
least a portion of the coker offgas to the at least one high shear
device; and a pump configured for delivering a liquid stream comprising
liquid carrier to the high shear device. In embodiments, the coker is a
delayed coker. In embodiments, the coker feedstock comprises residual. In
embodiments, the high shear device is operable to produce a dispersion of
the coker offgas in the liquid carrier, wherein the bubbles of coker
offgas in the dispersion have an average bubble diameter of less than 5,
4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1 μm. In embodiments, the bubbles
of coker offgas in the dispersion have a bubble diameter of less than 1
micron. In embodiments, the at least one rotor is rotatable at a tip
speed of at least 40 m/s.

[0024]Also disclosed is a system for producing value-added product from
pyrolysis, the system comprising: at least one high shear device
comprising at least one rotor and at least one complementarily-shaped
stator, wherein the at least one rotor is rotatable at a tip speed of at
least 22.9 m/s (4,500 ft/min), wherein the tip speed is defined as
πDn, where D is the diameter of the rotor and n is the frequency of
revolution; a steam cracker configured for producing pyrolysis gas from a
feedstock, the at least one high shear device in fluid communication with
a line configured for carrying at least a portion of the pyrolysis gas to
the at least one high shear device; and a pump configured for delivering
a liquid stream comprising liquid carrier to the high shear device. In
embodiments, the system further comprises a separator upstream of the at
least one high shear device for separating at least one component from
the pyrolysis gas. In embodiments, the steam cracker feedstock comprises
naphtha. In embodiments, the high shear device is operable to produce a
dispersion of the pyrolysis gas in the liquid carrier, wherein the
bubbles of pyrolysis gas in the dispersion have an average bubble
diameter of less than 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1 μm. In
embodiments, the bubbles of pyrolysis gas in the dispersion have a bubble
diameter of less than 1 micron. In embodiments, the at least one rotor is
rotatable at a tip speed of at least 40 m/s.

[0025]Certain embodiments of the above-described methods or systems
potentially provide overall cost reduction by providing for reduced
catalyst usage, permitting increased fluid throughput, permitting
operation at lower temperature and/or pressure, and/or reducing capital
and/or operating costs. These and other embodiments and potential
advantages will be apparent in the following detailed description and
drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0026]For a more detailed description of the preferred embodiment of the
present invention, reference will now be made to the accompanying
drawings, wherein:

[0027]FIG. 1 is a schematic of a high shear system according to an
embodiment of the present disclosure comprising external high shear
dispersing.

[0028]FIG. 2 is a longitudinal cross-section view of a high shear mixing
device suitable for use in embodiments of the system of FIG. 1.

[0029]FIG. 3 is a schematic of a suitable Refinery-Related Gas (RRG)
production apparatus 15A according to an embodiment of this disclosure.

[0030]FIG. 4 is a schematic of a suitable RRG production apparatus 15B
according to an embodiment of this disclosure.

[0031]FIG. 5 is a schematic of a suitable RRG production apparatus 15C
according to an embodiment of this disclosure.

[0032]FIG. 6 is a schematic of a suitable RRG production apparatus 15D
according to an embodiment of this disclosure.

[0033]FIG. 7 is a schematic of a suitable RRG production apparatus 15E
according to an embodiment of this disclosure.

[0034]FIG. 8 is a diagram of a method of producing value product from RRG
250 according to an embodiment of this disclosure.

[0035]FIG. 9 is a box diagram of a method of providing RRG 300A according
to an embodiment of this disclosure.

[0036]FIG. 10 is a schematic of a method of providing cracker feedstock
301A according to an embodiment of this disclosure.

[0037]FIG. 11 is a box diagram of a method of providing RRG 300B according
to an embodiment of this disclosure.

[0038]FIG. 12 is a box diagram of a method of providing RRG 300C according
to an embodiment of this disclosure.

[0039]FIG. 13 is box diagram of a method of providing RRG 300D according
to an embodiment of this disclosure.

[0040]FIG. 14 is a box diagram of a method 600A of adjusting the stability
and or the API gravity of crude oil according to an embodiment of this
disclosure.

NOTATION AND NOMENCLATURE

[0041]As used herein, the term `dispersion` refers to a liquefied mixture
that contains at least two distinguishable substances (or `phases`) that
will not readily mix and dissolve together. As used herein, a
`dispersion` comprises a `continuous` phase (or `matrix`), which holds
therein discontinuous droplets, bubbles, and/or particles of the other
phase or substance. The term dispersion may thus refer to foams
comprising gas bubbles suspended in a liquid continuous phase, emulsions
in which droplets of a first liquid are dispersed throughout a continuous
phase comprising a second liquid with which the first liquid is
immiscible, and continuous liquid phases throughout which solid particles
are distributed. As used herein, the term "dispersion" encompasses
continuous liquid phases throughout which gas bubbles are distributed,
continuous liquid phases throughout which solid particles (e.g., solid
catalyst) are distributed, continuous phases of a first liquid throughout
which droplets of a second liquid that is substantially insoluble in the
continuous phase are distributed, and liquid phases throughout which any
one or a combination of solid particles, immiscible liquid droplets, and
gas bubbles are distributed. Hence, a dispersion can exist as a
homogeneous mixture in some cases (e.g., liquid/liquid phase), or as a
heterogeneous mixture (e.g., gas/liquid, solid/liquid, or
gas/solid/liquid), depending on the nature of the materials selected for
combination.

[0042]The use of the term `refinery-related gas,` or the acronym `RRG,` is
intended to refer to any suitable gas obtained in an oil refinery or
obtained from extraction of crude oil or and/or associated gas from the
earth. Generally, the RRG comprises at least one of C1 to C8 compounds
and may contain hydrogen. In embodiments, the RRG comprises at least one
of C1 to C4 compounds and may contain hydrogen. For example, the RRG can
comprise one or more chosen from methane, ethane, propane, butane,
ethylene, propylene, butylene, carbon dioxide, carbon monoxide, and
hydrogen.

[0043]The term `gas oil` refers to middle-distillate petroleum fraction
with a boiling range of about 350° F. to 750° F., and may
include diesel fuel, kerosene, heating oil, and light fuel oil.

[0044]The term `gasoline` refers to a blend of naphthas and other refinery
products with sufficiently high octane and other desirable
characteristics to be suitable for use as fuel in internal combustion
engines.

[0045]Use of the phrase, `all or a portion of` is used herein to mean `all
or a percentage of the whole` or `all or some components of.`

DETAILED DESCRIPTION

[0046]Overview. A system and process for producing value-added products
from refinery-related gas (hereinafter RRG) comprises an external high
shear mechanical device to provide rapid contact and mixing of reactants
in a controlled environment in the reactor/mixer device. A reactor
assembly that comprises an external high shear device (HSD) or mixer as
described herein may decrease mass transfer limitations and thereby allow
the reaction, which may be catalytic, to more closely approach kinetic
and/or thermodynamic limitations. Enhanced mixing may also homogenize the
temperature within the reaction zone(s). Enhancing contact via the use of
high shear may permit increased throughput and/or the use of a decreased
amount of catalyst relative to conventional processes. The use of a HSD
may also provide for eliminating the use of catalyst entirely in some
instances.

[0047]High Shear System for Producing Value-Added Products from
Refinery-Related Gas. A high shear system 100 for producing value-added
products from refinery-related gas will be described with reference to
FIG. 1, which is a process flow diagram of an embodiment of a high shear
system 100. The basic components of a representative system include
external high shear device (HSD) 40 and pump 5. Each of these components
is further described in more detail below. Line 21 is connected to pump 5
for introducing reactants into pump 5. Line 13 connects pump 5 to HSD 40,
and line 19 carries product dispersion out of HSD 40. Additional
components or process steps can be incorporated between flow line 19 and
HSD 40, or ahead of pump 5 or HSD 40, if desired, as will become apparent
upon reading the description of the high shear process hereinbelow. For
example, line 20 can be connected to line 21 or line 13 from flow line 19
or reactor 10, such that fluid in flow line 19 or from vessel 10 may be
recycled to HSD 40. Product may be removed from system 100 via flow line
19. Flow line 19 is any line into which product dispersion (comprising at
least liquids and gases) and any unreacted reactants from HSD 40 flow.

[0048]System 100 may further comprise a vessel 10 and apparatus for
production of RRG 15, as described further hereinbelow. Line 22 is
configured to introduce dispersible gas (i.e., RRG) into HSD 40. Line 22
may introduce dispersible gas into HSD directly or may introduce RRG into
line 13. In embodiments, line 22 is connected with RRG production
apparatus 15. Alternatively, dispersible gas inlet line 22 is connected
to an RRG gas storage unit.

[0049]High Shear Device. External high shear device (HSD) 40, also
sometimes referred to as a high shear mixer, is configured for receiving
an inlet stream, via line 13, comprising reactants. Alternatively, HSD 40
may be configured for receiving the reactants via separate inlet lines.
Although only one HSD is shown in FIG. 1, it should be understood that
some embodiments of the system can comprise two or more HSDs arranged
either in series or parallel flow.

[0050]HSD 40 is a mechanical device that utilizes one or more generator
comprising a rotor/stator combination, each of which has a gap between
the stator and rotor. The gap between the rotor and the stator in each
generator set may be fixed or may be adjustable. HSD 40 is configured in
such a way that it is capable of effectively contacting the reactants
with the catalyst therein at rotational velocity. The HSD comprises an
enclosure or housing so that the pressure and temperature of the fluid
therein may be controlled.

[0051]High shear mixing devices are generally divided into three general
classes, based upon their ability to mix fluids. Mixing is the process of
reducing the size of particles or inhomogeneous species within the fluid.
One metric for the degree or thoroughness of mixing is the energy density
per unit volume that the mixing device generates to disrupt the fluid
particles. The classes are distinguished based on delivered energy
densities. Three classes of industrial mixers having sufficient energy
density to consistently produce mixtures or emulsions with particle sizes
in the range of submicron to 50 microns include homogenization valve
systems, colloid mills and high speed mixers. In the first class of high
energy devices, referred to as homogenization valve systems, fluid to be
processed is pumped under very high pressure through a narrow-gap valve
into a lower pressure environment. The pressure gradients across the
valve and the resulting turbulence and cavitation act to break-up any
particles in the fluid. These valve systems are most commonly used in
milk homogenization and can yield average particle sizes in the submicron
to about 1 micron range.

[0052]At the opposite end of the energy density spectrum is the third
class of devices referred to as low energy devices. These systems usually
have paddles or fluid rotors that turn at high speed in a reservoir of
fluid to be processed, which in many of the more common applications is a
food product. These low energy systems are customarily used when average
particle sizes of greater than 20 microns are acceptable in the processed
fluid.

[0053]Between the low energy devices and homogenization valve systems, in
terms of the mixing energy density delivered to the fluid, are colloid
mills and other high speed rotor-stator devices, which are classified as
intermediate energy devices. A typical colloid mill configuration
includes a conical or disk rotor that is separated from a complementary,
liquid-cooled stator by a closely-controlled rotor-stator gap, which is
commonly between 0.025 mm to 10 mm (0.001-0.40 inch). Rotors are usually
driven by an electric motor through a direct drive or belt mechanism. As
the rotor rotates at high rates, it pumps fluid between the outer surface
of the rotor and the inner surface of the stator, and shear forces
generated in the gap process the fluid. Many colloid mills with proper
adjustment achieve average particle sizes of 0.1 to 25 microns in the
processed fluid. These capabilities render colloid mills appropriate for
a variety of applications including colloid and oil/water-based emulsion
processing such as that required for cosmetics, mayonnaise, or
silicone/silver amalgam formation, to roofing-tar mixing.

[0054]The HSD comprises at least one revolving element that creates the
mechanical force applied to the reactants therein. The HSD comprises at
least one stator and at least one rotor separated by a clearance. For
example, the rotors can be conical or disk shaped and can be separated
from a complementarily-shaped stator. In embodiments, both the rotor and
stator comprise a plurality of circumferentially-spaced rings having
complementarily-shaped tips. A ring may comprise a solitary surface or
tip encircling the rotor or the stator. In embodiments, both the rotor
and stator comprise more than 2 circumferentially-spaced rings, more than
3 rings, or more than 4 rings. For example, in embodiments, each of three
generators comprises a rotor and stator each having 3 complementary
rings, whereby the material processed passes through 9 shear gaps or
stages upon traversing HSD 40. Alternatively, each of three generators
may comprise four rings, whereby the processed material passes through 12
shear gaps or stages upon passing through HSD 40. In some embodiments,
the stator(s) are adjustable to obtain the desired shear gap between the
rotor and the stator of each generator (rotor/stator set). Each generator
may be driven by any suitable drive system configured for providing the
desired rotation.

[0055]In some embodiments, HSD 40 comprises a single stage dispersing
chamber (i.e., a single rotor/stator combination; a single high shear
generator). In some embodiments, HSD 40 is a multiple stage inline
disperser and comprises a plurality of generators. In certain
embodiments, HSD 40 comprises at least two generators. In other
embodiments, HSD 40 comprises at least 3 generators. In some embodiments,
HSD 40 is a multistage mixer whereby the shear rate (which varies
proportionately with tip speed and inversely with rotor/stator gap width)
varies with longitudinal position along the flow pathway, as further
described hereinbelow.

[0056]According to this disclosure, at least one surface within HSD 40 may
be made of, impregnated with, or coated with a catalyst suitable for
catalyzing a desired reaction, as described in U.S. patent application
Ser. No. 12/476,415, which is hereby incorporated herein by reference for
all purposes not contrary to this disclosure. For example, in
embodiments, all or a portion of at least one rotor, at least one stator,
or at least one rotor/stator set (i.e., at least one generator) is made
of, coated with, or impregnated with a suitable catalyst. In some
applications, it may be desirable to utilize two or more different
catalysts. In such instances, a generator may comprise a rotor made of,
impregnated with, or coated with a first catalyst material, and the
corresponding stator of the generator may be made of, coated with, or
impregnated by a second catalyst material. Alternatively one or more
rings of the rotor may be made from, coated with, or impregnated with a
first catalyst, and one or more rings of the rotor may be made from,
coated with, or impregnated by a second catalyst. Alternatively one or
more rings of the stator may be made from, coated with, or impregnated
with a first catalyst, and one or more rings of the stator may be made
from, coated with, or impregnated by a second catalyst. All or a portion
of a contact surface of a stator, rotor, or both can be made from or
coated with catalytic material.

[0057]A contact surface of HSD 40 can be made from a porous sintered
catalyst material, such as platinum. In embodiments, a contact surface is
coated with a porous sintered catalytic material. In applications, a
contact surface of HSD 40 is coated with or made from a sintered material
and subsequently impregnated with a desired catalyst. The sintered
material can be a ceramic or can be made from metal powder, such as, for
example, stainless steel or pseudoboehmite. The pores of the sintered
material may be in the micron or the submicron range. The pore size can
be selected such that the desired flow and catalytic effect are obtained.
Smaller pore size may permit improved contact between fluid comprising
reactants and catalyst. By altering the pore size of the porous material
(ceramic or sintered metal), the available surface area of the catalyst
can be adjusted to a desired value. The sintered material may comprise,
for example, from about 70% by volume to about 99% by volume of the
sintered material or from about 80% by volume to about 90% by volume of
the sintered material, with the balance of the volume occupied by the
pores.

[0058]In embodiments, the rings defined by the tips of the rotor/stator
contain no openings (i.e. teeth or grooves) such that substantially all
of the reactants are forced through the pores of the sintered material,
rather than being able to bypass the catalyst by passing through any
openings or grooves which are generally present in conventional
dispersers. In this manner, for example, a reactant will be forced
through the sintered material, thus forcing contact with the catalyst.

[0059]In embodiments, the sintered material of which the contact surface
is made comprises stainless steel or bronze. The sintered material
(sintered metal or ceramic) may be passivated. A catalyst may then be
applied thereto. The catalyst may be applied by any means known in the
art. The contact surface may then be calcined to yield the metal oxide
(e.g. stainless steel). The first metal oxide (e.g., the stainless steel
oxide) may be coated with a second metal and calcined again. For example,
stainless steel oxide may be coated with aluminum and calcined to produce
aluminum oxide. Subsequent treatment may provide another material. For
example, the aluminum oxide may be coated with silicon and calcined to
provide silica. Several calcining/coating steps may be utilized to
provide the desired contact surface and catalyst(s). In this manner, the
sintered material which either makes up the contact surface or coats the
contact surface may be impregnated with a variety of catalysts. Another
coating technique, for example, is metal vapor deposition or chemical
vapor deposition, such as typically used for coating silicon wafers with
metal.

[0060]In embodiments, a sintered metal contact surface (e.g., of the rotor
or the stator) is treated with a material. For example, tetra ethyl ortho
silicate (TEOS). Following vacuum evaporation, TEOS may remain in surface
pores. Calcination may be used to convert the TEOS to silica. This
impregnation may be repeated for all desired metal catalysts. Upon
formation, coating, or impregnation, the catalyst(s) may be activated
according to manufacturer's protocol. For example, catalysts may be
activated by contacting with an activation gas, such as hydrogen. The
base material may be silicon or aluminum which, upon calcination, is
converted to alumina or silica respectively. Suitable catalysts,
including without limitation, rhenium, palladium, rhodium, etc. can
subsequently be impregnated into the pores.

[0061]In some embodiments, the minimum clearance (shear gap width) between
the stator and the rotor is in the range of from about 0.025 mm (0.001
inch) to about 3 mm (0.125 inch). In some embodiments, the minimum
clearance (shear gap width) between the stator and the rotor is in the
range of from about 1 μm (0.00004 inch) to about 3 mm (0.012 inch). In
some embodiments, the minimum clearance (shear gap width) between the
stator and the rotor is less than about 10 μm (0.0004 inch), less than
about 50 μm (0.002 inch), less than about 100 μm (0.004 inch), less
than about 200 λm (0.008 inch), less than about 400 μm (0.016
inch). In certain embodiments, the minimum clearance (shear gap width)
between the stator and rotor is about 1.5 mm (0.06 inch). In certain
embodiments, the minimum clearance (shear gap width) between the stator
and rotor is about 0.2 mm (0.008 inch). In certain configurations, the
minimum clearance (shear gap) between the rotor and stator is at least
1.7 mm (0.07 inch). The shear rate produced by the HSD may vary with
longitudinal position along the flow pathway. In some embodiments, the
rotor is set to rotate at a speed commensurate with the diameter of the
rotor and the desired tip speed. In some embodiments, the HSD has a fixed
clearance (shear gap width) between the stator and rotor. Alternatively,
the HSD has adjustable clearance (shear gap width). The shear gap may be
in the range of from about 5 micrometers (0.0002 inch) and about 4 mm
(0.016 inch).

[0062]Tip speed is the circumferential distance traveled by the tip of the
rotor per unit of time. Tip speed is thus a function of the rotor
diameter and the rotational frequency. Tip speed (in meters per minute,
for example) may be calculated by multiplying the circumferential
distance transcribed by the rotor tip, 2πR, where R is the radius of
the rotor (meters, for example) times the frequency of revolution (for
example revolutions per minute, rpm). The frequency of revolution may be
greater than 250 rpm, greater than 500 rpm, greater than 1000 rpm,
greater than 5000 rpm, greater than 7500 rpm, greater than 10,000 rpm,
greater than 13,000 rpm, or greater than 15,000 rpm. The rotational
frequency, flow rate, and temperature may be adjusted to get a desired
product profile. If channeling should occur, and some reactants pass
through unreacted, the rotational frequency may be increased to minimize
undesirable channeling. Alternatively or additionally, unreacted
reactants may be introduced into a second or subsequent HSD 40, or a
portion of the unreacted reactants may be separated from the products and
recycled to HSD 40.

[0063]HSD 40 may have a tip speed in excess of 22.9 m/s (4500 ft/min) and
may exceed 40 m/s (7900 ft/min), 50 m/s (9800 ft/min), 100 m/s (19,600
ft/min), 150 m/s (29,500 ft/min), 200 m/s (39,300 ft/min), or even 225
m/s (44,300 ft/min) or greater in certain applications. For the purpose
of this disclosure, the term `high shear` refers to mechanical rotor
stator devices (e.g., colloid mills or rotor-stator dispersers) that are
capable of tip speeds in excess of 5.1 m/s. (1000 ft/min) and require an
external mechanically driven power device to drive energy into the stream
of products to be reacted. By contacting the reactants with the rotating
members, which can be made from, coated with, or impregnated with
stationary catalyst, significant energy is transferred to the reaction.
Especially in instances where the reactants are gaseous, the energy
consumption of the HSD 40 will be very low. The temperature may be
adjusted to control the product profile and to extend catalyst life.

[0064]In some embodiments, HSD 40 is capable of delivering at least 300
L/h at a tip speed of at least 22.9 m/s (4500 ft/min). The power
consumption may be about 1.5 kW. HSD 40 combines high tip speed with a
very small shear gap to produce significant shear on the material being
processed. The amount of shear will be dependent on the viscosity of the
fluid in HSD 40. Accordingly, a local region of elevated pressure and
temperature is created at the tip of the rotor during operation of HSD
40. In some cases the locally elevated pressure is about 1034.2 MPa
(150,000 psi). In some cases the locally elevated temperature is about
500° C. In some cases, these local pressure and temperature
elevations may persist for nano or pico seconds.

[0065]An approximation of energy input into the fluid (kW/L/min) can be
estimated by measuring the motor energy (kW) and fluid output (L/min). As
mentioned above, tip speed is the velocity (ft/min or m/s) associated
with the end of the one or more revolving elements that is creating the
mechanical force applied to the fluid. In embodiments, the energy
expenditure of HSD 40 is greater than 1000 watts per cubic meter of fluid
therein. In embodiments, the energy expenditure of HSD 40 is in the range
of from about 3000 W/m3 to about 7500 kW/m3. In embodiments,
the energy expenditure of HSD 40 is in the range of from about 3000
W/m3 to about 7500 W/m3. The actual energy input needed is a
function of what reactions are occurring within the HSD, for example,
endothermic and/or exothermic reaction(s), as well as the mechanical
energy required for dispersing and mixing feedstock materials. In some
applications, the presence of exothermic reaction(s) occurring within the
HSD mitigates some or substantially all of the reaction energy needed
from the motor input. When dispersing a gas in a liquid, the energy
requirements are significantly less.

[0066]The shear rate is the tip speed divided by the shear gap width
(minimal clearance between the rotor and stator). The shear rate
generated in HSD 40 may be in the greater than 20,000 s-1. In some
embodiments the shear rate is at least 40,000 s-1. In some
embodiments the shear rate is at least 100,000 s-1. In some
embodiments the shear rate is at least 500,000 s-1. In some
embodiments the shear rate is at least 1,000,000 s-1. In some
embodiments the shear rate is at least 1,600,000 s-1. In some
embodiments the shear rate is at least 3,000,000 s-1. In some
embodiments the shear rate is at least 5,000,000 s-1. In some
embodiments the shear rate is at least 7,000,000 s-1. In some
embodiments the shear rate is at least 9,000,000 s-1. In embodiments
where the rotor has a larger diameter, the shear rate may exceed about
9,000,000 s-1. In embodiments, the shear rate generated by HSD 40 is
in the range of from 20,000 s-1 to 10,000,000 s-1. For example,
in one application the rotor tip speed is about 40 m/s (7900 ft/min) and
the shear gap width is 0.0254 mm (0.001 inch), producing a shear rate of
1,600,000 s-1. In another application the rotor tip speed is about
22.9 m/s (4500 ft/min) and the shear gap width is 0.0254 mm (0.001 inch),
producing a shear rate of about 901,600 s-1.

[0068]In some embodiments, each stage of the external HSD has
interchangeable mixing tools, offering flexibility. For example, the DR
2000/4 DISPAX REACTOR® of IKA® Works, Inc. Wilmington, N.C. and
APV North America, Inc. Wilmington, Mass., comprises a three stage
dispersing module. This module may comprise up to three rotor/stator
combinations (generators), with choice of fine, medium, coarse, and
super-fine for each stage. This allows for variance of shear rate along
the direction of flow. In some embodiments, each of the stages is
operated with super-fine generator. In some embodiments, at least one of
the generator sets has a rotor/stator minimum clearance (shear gap width)
of greater than about 5 mm (0.2 inch). In some embodiments, at least one
of the generator sets has a rotor/stator minimum clearance (shear gap
width) of about 0.2 mm (0.008 inch). In alternative embodiments, at least
one of the generator sets has a minimum rotor/stator clearance of greater
than about 1.7 mm (0.07 inch).

[0069]In embodiments, a scaled-up version of the DISPAX REACTOR® is
utilized. For example, in embodiments HSD 40 comprises a SUPER DISPAX
REACTOR® DRS 2000. The HSD unit may be a DR 2000/50 unit, having a
flow capacity of 125,000 liters per hour, or a DRS 2000/50 having a flow
capacity of 40,000 liters/hour. Because residence time is increased in
the DRS unit, the fluid therein is subjected to more shear. Referring now
to FIG. 2, there is presented a longitudinal cross-section of a suitable
HSD 200. HSD 200 of FIG. 2 is a dispersing device comprising three stages
or rotor-stator combinations, 220, 230, and 240. The rotor-stator
combinations may be known as generators 220, 230, 240 or stages without
limitation. Three rotor/stator sets or generators 220, 230, and 240 are
aligned in series along drive shaft 250.

[0070]First generator 220 comprises rotor 222 and stator 227. Second
generator 230 comprises rotor 223, and stator 228. Third generator 240
comprises rotor 224 and stator 229. For each generator the rotor is
rotatably driven by input 250 and rotates about axis 260 as indicated by
arrow 265. The direction of rotation may be opposite that shown by arrow
265 (e.g., clockwise or counterclockwise about axis of rotation 260).
Stators 227, 228, and 229 may be fixably coupled to the wall 255 of HSD
200. As mentioned hereinabove, each rotor and stator may comprise rings
of complementarily-shaped tips, leading to several shear gaps within each
generator.

[0071]As discussed above, a contact surface of the HSD 40 may be made
from, coated with, or impregnated by a suitable catalyst which catalyzes
the desired reaction. In embodiments, a contact surface of one ring of
each rotor or stator is made from, coated with, or impregnated with a
different catalyst than the contact surface of another ring of the rotor
or stator. Alternatively or additionally, a contact surface of one ring
of the stator may be made from coated with or impregnated by a different
catalyst than the complementary ring on the rotor. The contact surface
may be at least a portion of the rotor, at least a portion of the stator,
or both. The contact surface may comprise, for example, at least a
portion of the outer surface of a rotor, at least a portion of the inner
surface of a stator, or at least a portion of both.

[0072]As mentioned hereinabove, each generator has a shear gap width which
is the minimum distance between the rotor and the stator. In the
embodiment of FIG. 2, first generator 220 comprises a first shear gap
225; second generator 230 comprises a second shear gap 235; and third
generator 240 comprises a third shear gap 245. In embodiments, shear gaps
225, 235, 245 have widths in the range of from about 0.025 mm to about 10
mm. Alternatively, the process comprises utilization of an HSD 200
wherein the gaps 225, 235, 245 have a width in the range of from about
0.5 mm to about 2.5 mm. In certain instances the shear gap width is
maintained at about 1.5 mm. Alternatively, the width of shear gaps 225,
235, 245 are different for generators 220, 230, 240. In certain
instances, the width of shear gap 225 of first generator 220 is greater
than the width of shear gap 235 of second generator 230, which is in turn
greater than the width of shear gap 245 of third generator 240. As
mentioned above, the generators of each stage may be interchangeable,
offering flexibility. HSD 200 may be configured so that the shear rate
remains the same or increases or decreases stepwise longitudinally along
the direction of the flow 260.

[0073]Generators 220, 230, and 240 may comprise a coarse, medium, fine,
and super-fine characterization, having different numbers of
complementary rings or stages on the rotors and complementary stators.
Although generally less desirable, rotors 222, 223, and 224 and stators
227, 228, and 229 may be toothed designs. Each generator may comprise two
or more sets of complementary rotor-stator rings. In embodiments, rotors
222, 223, and 224 comprise more than 3 sets of complementary rotor/stator
rings. In embodiments, the rotor and the stator comprise no teeth, thus
forcing the reactants to flow through the pores of a sintered material.

[0074]HSD 40 may be a large or small scale device. In embodiments, HSD 40
is used to process from less than 10 tons per hour to 50 tons per hour.
In embodiments, HSD 40 processes 10 tons/h, 20 tons/h, 30 ton/hr, 40
tons/h, 50 tons/h, or more than 50 tons/h. Large scale units may produce
1000 gal/h (24 barrels/h). The inner diameter of the rotor may be any
size suitable for a desired application. In embodiments, the inner
diameter of the rotor is from about 12 cm (4 inch) to about 40 cm (15
inch). In embodiments, the diameter of the rotor is about 6 cm (2.4
inch). In embodiments, the outer diameter of the stator is about 15 cm
(5.9 inch). In embodiments, the diameter of the stator is about 6.4 cm
(2.5 inch). In some embodiments the rotors are 60 cm (2.4 inch) and the
stators are 6.4 cm (2.5 inch) in diameter, providing a clearance of about
4 mm. In certain embodiments, each of three stages is operated with a
super-fine generator comprising a number of sets of complementary
rotor/stator rings.

[0075]HSD 200 is configured for receiving at inlet 205 a fluid mixture
from line 13. The mixture comprises reactants. The reactants comprise
RRG. In embodiments, at least one reactant is gaseous and at least one
reactant is liquid. Feed stream entering inlet 205 is pumped serially
through generators 220, 230, and then 240, such that product is formed.
Product exits HSD 200 via outlet 210 (and line 19 of FIG. 1). The rotors
222, 223, 224 of each generator rotate at high speed relative to the
fixed stators 227, 228, 229, providing a high shear rate. The rotation of
the rotors pumps fluid, such as the feed stream entering inlet 205,
outwardly through the shear gaps (and, if present, through the spaces
between the rotor teeth and the spaces between the stator teeth),
creating a localized high shear condition. High shear forces exerted on
fluid in shear gaps 225, 235, and 245 (and, when present, in the gaps
between the rotor teeth and the stator teeth) through which fluid flows
process the fluid and create product. The product may comprise a
dispersion of unreacted or product gas in a continuous phase of liquid
(e.g., liquid product and carrier/catalyst). Product exits HSD 200 via
high shear outlet 210 (and line 19 of FIG. 1).

[0076]As mentioned above, in certain instances, HSD 200 comprises a DISPAX
REACTOR® of IKA® Works, Inc. Wilmington, N.C. and APV North
America, Inc. Wilmington, Mass. Several models are available having
various inlet/outlet connections, horsepower, tip speeds, output rpm, and
flow rate. Selection of the HSD will depend on throughput selection and
desired particle, droplet or bubble size in dispersion in line 10 (FIG.
1) exiting outlet 210 of HSD 200. IKA® model DR 2000/4, for example,
comprises a belt drive, 4M generator, PTFE sealing ring, inlet flange
25.4 mm (1 inch) sanitary clamp, outlet flange 19 mm (3/4 inch) sanitary
clamp, 2HP power, output speed of 7900 rpm, flow capacity (water)
approximately 300-700 L/h (depending on generator), a tip speed of from
9.4-41 m/s (1850 ft/min to 8070 ft/min). Scale up may be performed by
using a plurality of HSDs, or by utilizing larger HSDs. Scale-up using
larger models is readily performed, and results from larger HSD 40 units
may provide improved efficiency in some instances relative to the
efficiency of lab-scale devices. The large scale unit may be a
DISPAX® 2000/unit. For example, the DRS 2000/5 unit has an inlet size
of 51 mm (2 inches) and an outlet of 38 mm (1.5 inches).

[0077]In embodiments wherein strong acid is utilized as carrier, HSD 40
and other portions of system 100 may be made from refractory/corrosion
resistant materials. For example, Inconel® alloys, tungsten or
Hastelloy® materials may be used.

[0078]Vessel. Vessel or reactor 10 is any type of vessel in which a
multiphase reaction can be propagated to carry out the above-described
conversion reaction(s). For instance, a continuous or semi-continuous
stirred tank reactor, or one or more batch reactors may be employed in
series or in parallel. In some applications vessel 10 may be a tower
reactor, and in others a tubular reactor or multi-tubular reactor. A
catalyst inlet line may be connected to vessel 10 for receiving a
catalyst solution or slurry during operation of the system. In
embodiments where a significant reaction occurs in HSD 40, vessel 10 may
comprise one or more fractionators suitable for separating components
selected from unreacted and light gas, liquid carrier, catalyst, and
value-added product. Vessel 10 may comprise outlet lines for unreacted or
light product gas 16, oxygenate product 17 and carrier fluid 20. In
embodiments, system 100 comprises distinct apparatus configured to
separate unreacted and/or light gas from value-added product, to separate
carrier fluid from value-added product, to separate catalyst from
value-added product or to separate some combination thereof.

[0079]Vessel 10 may include one or more of the following components:
stirring system, heating and/or cooling capabilities, pressure
measurement instrumentation, temperature measurement instrumentation, one
or more injection points, and level regulator, as are known in the art of
reaction vessel design. For example, a stirring system may include a
motor driven mixer. A heating and/or cooling apparatus may comprise, for
example, a heat exchanger. Alternatively, as much of the reaction may
occur within HSD 40 in some embodiments, vessel 10 may serve primarily as
a storage vessel in some cases. Although generally less desired, in some
applications vessel 10 may be omitted, particularly if multiple high
shears/reactors are employed in series, as further described below.

[0080]RRG Production Apparatus. Dispersible refinery-related gas or RRG
may be any suitable refinery-related gas comprising at least one of C1-C8
compounds. The RRG typically comprises C1 to C4 fractions and hydrogen.
For example, RRG may comprise any combination of methane, ethane,
propane, butane, ethylene, propylene, butylene, carbon monoxide, and
carbon dioxide. RRG may also comprise hydrogen and/or sulfur compounds,
such as hydrogen sulfide. Most desirably, RRG comprises negative value
gas from a refinery. As used herein, negative value gas is a gas whose
disposal has a cost and/or is not profitable, such as a gas normally
flared or treated in an expensive manner, perhaps prior to flaring. In
embodiments, gases used as RRG are those gases typically conventionally
used as boiler fuel or flared. In embodiments, RRG comprises gas
conventionally introduced into a gas plant of a refinery. In embodiments,
RRG comprises pyrolysis gas, coker offgas, FCC offgas, light FCC offgas,
associated gas, or a combination thereof.

[0081]FIG. 3 is a schematic of a typical refinery 15A. RRG production
apparatus 15 may be equipment as shown in refinery 15A, or any
combination or subset thereof, including multiple of the units indicated.
Such equipment and processes are described, for example, in OSHA
Technical Manual TED 01-00-015; Section IV, Chapter 2. In embodiments,
RRG is derived from or comprises any gas shown directed to the gas plant
in FIG. 3. In embodiments, RRG is separated from a crude oil (i.e., as
associated gas). In embodiments, RRG is derived from or comprises a gas
produced during cracking. In embodiments, RRG is derived from or
comprises a gas produced during thermal cracking. For example, in
embodiments, RRG is derived from or comprises coker offgas produced by
thermal cracking in a coking operation. In embodiments, RRG is derived
from or comprises a gas produced during catalytic cracking. In
embodiments, RRG is derived from or comprises a gas produced during fluid
catalytic cracking. In embodiments, RRG comprises light FCC offgas. RRG
production apparatus 15 may be catalytic cracking apparatus known in the
art from which an offgas is obtained. In embodiments, RRG production
apparatus 15 is any FCC apparatus known in the art for fluid catalytic
cracking. For example, FIG. 4 is a schematic of a suitable RRG production
apparatus 15B. Some portion of apparatus 15B may be used to provide RRG.
In the embodiment of 15B, RRG production apparatus 15B is a FCC system
from which an offgas is produced. In embodiments, one or more component
of the offgas indicated in FIG. 4 is removed and the remaining gas is
utilized as RRG. Any FCC vapor recovery unit known in the art may be used
as RRG production apparatus. For example, the offgas of FCC system 15B in
FIG. 4 may be fractionated via a system or a portion of the system
similar to that of 15C in FIG. 5 prior to use as RRG.

[0082]In embodiments, RRG production apparatus 15 comprises steam cracking
apparatus from which pyrolysis gas is obtained. Various suitable steam
cracking apparatus are known in the art. FIG. 6 is a schematic of a
suitable apparatus 15D (i.e. the equipment upstream of the hydrotreating
and BTX extraction stages of FIG. 6) for producing pyrolysis gas. In
embodiments, RRG production apparatus comprises a steam cracker and may
further comprise a separator, as indicated in FIG. 6. In such instances,
C6+ gas from a steam cracker, or C6 fraction, C6-C8 or C8+ fraction from
a separator may be used as RRG.

[0083]In embodiments, RRG production apparatus 15 comprises coking
apparatus, from which coker offgas is obtained/derived. Various suitable
coking apparatus are known in the art. For example, a RRG production
apparatus 15E as indicated in FIG. 7 or some portion thereof may be
utilized in high shear system 100.

[0084]Heat Transfer Devices. Internal or external heat transfer devices
for heating the fluid to be treated are also contemplated in variations
of the system. For example, the reactants may be preheated via any method
known to one skilled in the art. Some suitable locations for one or more
such heat transfer devices are between pump 5 and HSD 40, between HSD 40
and flow line 19, and between flow line 19 and pump 5 when fluid in flow
line 19 is recycled to HSD 40. HSD 40 may comprise an inner shaft which
may be cooled, for example water-cooled, to partially or completely
control the temperature within HSD 40. Some non-limiting examples of such
heat transfer devices are shell, tube, plate, and coil heat exchangers,
as are known in the art.

[0085]Pumps. Pump 5 is configured for either continuous or semi-continuous
operation, and may be any suitable pumping device that is capable of
providing controlled flow through HSD 40 and system 100. In applications
pump 5 provides greater than 202.65 kPa (2 atm) pressure or greater than
303.97 kPa (3 atm) pressure. Pump 5 may be a Roper Type 1 gear pump,
Roper Pump Company (Commerce Georgia) Dayton Pressure Booster Pump Model
2P372E, Dayton Electric Co (Niles, Ill.) is one suitable pump.
Preferably, all contact parts of the pump comprise stainless steel, for
example, 316 stainless steel. In some embodiments of the system, pump 5
is capable of pressures greater than about 2026.5 kPa (20 atm). In
addition to pump 5, one or more additional, high pressure pumps may be
included in the system illustrated in FIG. 1. For example, a booster
pump, which may be similar to pump 5, may be included between HSD 40 and
flow line 19 for boosting the pressure into flow line 19.

[0086]High Shear Process for Producing Value-Added Products from
Refinery-Related Gas. A process for producing value-added products from
refinery-related gas will be described with respect to FIG. 8 which is a
flow diagram of a high shear process 250 according to this disclosure.
Process 250 comprises providing refinery-related gas 300; intimately
mixing RRG with carrier and/or catalyst at high shear to form a
dispersion and a product comprising value-added product 400; and
separating unreacted gas, carrier and/or catalyst and value-added product
500. Process 250 may further comprise subjecting light gas to high shear
600.

[0087]Providing Refinery-Related Gas, RRG. Providing a refinery-related
gas (RRG) 300 may comprise obtaining or producing any refinery-related
gas that is conventionally sent to a gas plant. Alternatively or
additionally, providing a refinery-related gas may comprise obtaining an
associated gas. The modern petroleum refinery utilized for petroleum
refining, also called oil refining, utilizes a series of core processes
and process units that provide clean gasoline and low sulfur diesel fuel.
Various offgases are produced in the refining process. The RRG may
comprise pyrolysis gas, FCC offgas, coker offgas, associated gas or any
combination thereof Preferably, the RRG is a `negative-value gas` which
is conventionally either flared or, when not suitable for flaring,
converted at expense to a less undesirable product. The RRG may comprise
olefins. Desirably, RRG comprises at least one C1 to C8 compound,
hydrogen, or some combination thereof. In embodiments, RRG comprises at
least one selected from C1 through C4 compounds and hydrogen.

[0088]The RRG may comprise a blast furnace gas having the following or a
similar composition: 40-50% (e.g. ˜46%) N2, 20-25% (e.g.
˜24%) CO, 20-30% (e.g. ˜26%) CO2, 1-5% (e.g. 4%)
H2, and minor amounts (e.g. less than ˜4%) of O2 and/or
CH4. The hydrocarbon types in FCC feed are broadly classified as
paraffin's, olefins, naphthenes and aromatics (PONA). A description of
gases that might conventionally be used as fuel or flared in a refinery
operation, and thus suitable for use as RRG according to this disclosure,
is provided in Petroleum Refinery Distillation second edition by R. N.
Watkins (ISBN 0-87201-672-2), which is hereby incorporated herein in its
entirety for all purposes not contradictory to this disclosure.

[0089]An embodiment for providing refinery-related gas is depicted in the
flow diagram of FIG. 9, which is a flow diagram of a method of providing
refinery-related gas 300A, wherein the RRG comprises offgas from
catalytic cracking (CC). It is noted, however, that the RRG may comprise
offgas from thermal (i.e., not catalytic) cracking Catalytic cracking is
the process of breaking up heavier hydrocarbon molecules into lighter
hydrocarbon fractions by use of heat and catalysts. The method of
providing RRG 300A in FIG. 9 comprises providing CC feedstock 301,
catalytically cracking the CC feedstock 302, and separating CC offgas
from CC products 303. FIG. 10 is a schematic of a suitable process 301A
for providing CC feedstock. The CC feedstock may comprise atmospheric gas
oil, AGO, and/or vacuum gas oil, VGO. Method 301A for providing CC
feedstock comprises providing crude oil 304, desalting the crude oil 305,
distilling the desalted crude oil at atmospheric pressure 306, and
distilling the atmospheric tower residue from 306 under vacuum to obtain
CC feedstock 307.

[0090]Providing crude oil 304 comprises providing one or more crude oils
via methods known in the art. Crude oils are naturally occurring complex
mixtures of hydrocarbons that typically include small quantities of
sulfur, nitrogen, and oxygen derivatives of hydrocarbons as well as trace
metals. Crude oils contain many different hydrocarbon compounds that vary
in appearance and composition from one oil field to another. Crude oils
range in consistency from water to tar-like solids, and in color from
clear to black. An `average` crude oil contains about 84% carbon, 14%
hydrogen, 1%-3% sulfur, and less than 1% each of nitrogen, oxygen,
metals, and salts. Crude oils are generally classified as paraffinic,
naphthenic, or aromatic, based on the predominant proportion of similar
hydrocarbon molecules. Mixed-base crudes contain varying amounts of each
type of hydrocarbon. Refinery crude base stocks usually contain mixtures
of two or more different crude oils.

[0091]Relatively simple crude oil assays are used to classify crude oils
as paraffinic, naphthenic, aromatic, or mixed. One assay method (United
States Bureau of Mines) is based on distillation, and another method (UOP
"K" factor) is based on gravity and boiling points. More comprehensive
crude assays may be utilized to estimate the value of the crude (i.e.,
yield and quality of useful products) and processing parameters. Crude
oils are typically grouped according to yield structure.

[0092]Crude oils are also defined in terms of API (American Petroleum
Institute) gravity. API gravity is an arbitrary scale expressing the
density of petroleum products. The higher the API gravity, the lighter
the crude. For example, light crude oils have high API gravities and low
specific gravities. Crude oils with low carbon, high hydrogen, and high
API gravity are usually rich in paraffins and tend to yield greater
proportions of gasoline and light petroleum products, while those with
high carbon, low hydrogen, and low API gravities are usually rich in
aromatics.

[0093]Crude oils that contain appreciable quantities of hydrogen sulfide
or other reactive sulfur compounds are referred to as `sour.` Crude oils
containing less sulfur are referred to as `sweet.` A notable exceptions
to this rule are West Texas crude oils, which are always considered
`sour` regardless of their hydrogen sulfide content, and Arabian
high-sulfur crudes, which are not considered `sour` because the sulfur
compounds therein are not highly reactive. Providing crude oil 304 may
comprise providing one or more selected from sweet crude oils, sour crude
oils, low API crude oils, high API crude oils, medium API crude oils,
paraffinic crude oils, naphthenic crude oils, aromatic crude oils, mixed
crude oils, or any combination thereof. Table 1 shows typical
characteristics, properties, and gasoline potential of various crude
oils.

[0094]Providing CC feedstock may comprise desalting the provided crude.
Desalting may be performed as known in the art to remove salt, water and
other contaminants from the crude oil prior to distillation in one or
more atmospheric tower. Providing CC feedstock may further comprise one
or more steps of distilling the crude oil. Crude oil fractionation
(distillation) is the separation of crude oil in atmospheric and vacuum
distillation towers into groups of hydrocarbon compounds of differing
boiling-point ranges called `fractions` or `cuts.` Fractionation
separates the crude oil into various fractions or straight-run cuts by
distillation in atmospheric and vacuum towers. The main fractions or
`cuts` obtained have specific boiling-point ranges and can be classified
in order of decreasing volatility into gases, light distillates, middle
distillates, gas oils, and residuum.

[0096]The desalted crude feedstock can be preheated using recovered
process heat. The feedstock can be introduced into a direct-fired crude
charge heater where it is fed into a vertical distillation column just
above the bottom, at pressures slightly above atmospheric and at
temperatures ranging from 650° F. to 700° F. (heating crude
oil above these temperatures may cause undesirable thermal cracking). All
but the heaviest fractions flash into vapor. As the hot vapor rises in
the tower, its temperature is reduced. Heavy fuel oil or asphalt residue
is taken from the bottom. At successively higher points on the tower, the
various major products including lubricating oil, heating oil, kerosene,
gasoline, and uncondensed gases (which condense at lower temperatures)
may be drawn off.

[0097]The fractionating tower used for atmospheric distillation can be any
distillation column known in the art. The fractionating tower may
comprise a steel cylinder about 120 feet high, containing horizontal
steel trays for separating and collecting the liquids. At each tray,
vapors from below enter perforations and bubble caps. The perforation and
bubble caps permit the vapors to bubble through the liquid on the tray,
causing some condensation at the temperature of that tray. An overflow
pipe can serve to drain the condensed liquids from each tray back to the
tray below, where the higher temperature causes re-evaporation. The
evaporation, condensing, and scrubbing operation is repeated many times
until the desired degree of product purity is reached. Side streams from
certain trays are then taken off to obtain the desired fractions.
Products ranging from uncondensed fixed gases at the top to heavy fuel
oils at the bottom can be continuously extracted from a fractionating
tower. Steam may be used in towers to lower the vapor pressure and create
a partial vacuum. The distillation process separates the major
constituents of crude oil into so-called straight-run products. Sometimes
crude oil is `topped` by distilling off only the lighter fractions,
leaving a heavy residue that is often distilled further under high
vacuum.

[0098]Distilling under vacuum 307 may be performed by any method known in
the art. In embodiments, vacuum distilling 307 comprises fractionating
the atmospheric tower residue via vacuum distillation into gas oil, light
vacuum distillate, heavy vacuum distillate, vacuum resid, or a
combination thereof. Vacuum distillation is the distillation of petroleum
under vacuum which reduces the boiling temperature sufficiently to
prevent cracking or decomposition of the feedstock. In embodiments, the
CC feedstock comprises gas oil from atmospheric and/or vacuum distilling,
light vacuum distillate, heavy vacuum distillate, or a combination
thereof.

[0099]In vacuum distilling, in order to further distill the residuum or
topped crude from the atmospheric distillation tower at higher
temperatures, reduced pressure is utilized to prevent thermal cracking
Vacuum distilling may be performed in one or more vacuum distillation
towers. The principles of vacuum distillation resemble those of
fractional distillation and the equipment is also similar, except that
larger-diameter columns may be used to maintain comparable vapor
velocities at the reduced pressures. The internal designs of the vacuum
tower may be different from the atmospheric distillation tower in that
random packing and demister pads may be used instead of trays. A typical
first-phase vacuum tower may be used to produce gas oils, lubricating-oil
base stocks, and heavy residual for propane deasphalting. Deasphalting is
a process of removing asphaltic materials from reduced crude using liquid
propane to dissolve nonasphaltic compounds. A second-phase tower
operating at lower vacuum may be used to distill surplus residuum from
the atmospheric tower, which is not used for lube-stock processing, and
surplus residuum from the first vacuum tower not used for deasphalting.
One or more vacuum tower can be used to separate the catalytic cracking
feedstock from surplus residuum.

[0100]Providing RRG may further comprise subjecting the CC feedstock to
catalytic cracking 302. Catalytic cracking breaks complex hydrocarbons
into simpler molecules in order to increase the quality and quantity of
lighter, more desirable products and decrease the amount of residuals.
This process rearranges the molecular structure of hydrocarbon compounds
to convert heavy hydrocarbon feedstock into lighter fractions such as
kerosene, gasoline, LPG, heating oil, and petrochemical feedstock.

[0101]Catalytic cracking is similar to thermal cracking except that
catalysts facilitate the conversion of the heavier molecules into lighter
products. Use of a catalyst (i.e., a material that assists a chemical
reaction but does not take part in it) in the cracking reaction increases
the yield of improved-quality products under much less severe operating
conditions than in thermal cracking. Typical temperatures are from
850° F. to 950° F. at much lower pressures of 10 to 20 psi.
The catalysts used in the cracking unit may be solid materials (e.g.,
zeolite, aluminum hydrosilicate, treated bentonite clay, fuller's earth,
bauxite, and silica-alumina) that come in the form of powders, beads,
pellets or are shaped materials called extrudites. In catalytic cracking,
catalytic cracking feedstock reacts with catalyst and cracks into
different hydrocarbons; catalyst is reactivated by burning off coke; and
the cracked hydrocarbon products are separated into various products.

[0102]The RRG can be obtained or derived via any of the three types of
catalytic cracking processes: fluid catalytic cracking (FCC), moving-bed
catalytic cracking, and Thermofor catalytic cracking (TCC). The catalytic
cracking process is very flexible, and operating parameters can be
adjusted to meet changing product demand. The offgas composition utilized
as RRG may vary depending on operating parameters of the cracking. In
addition to cracking, catalytic activities include dehydrogenation,
hydrogenation, and/or isomerization. Table 2 indicates the feedstock and
typical products of catalytic cracking processes. As indicated, all or a
portion of the off gas from catalytic cracking may, according to this
disclosure, be utilized as RRG.

[0103]In embodiments, providing RRG comprises providing offgas from a
fluid catalytic cracker, FFC, for example a FCC as shown in FIG. 4. Fluid
catalytic cracking (FCC) is the most important conversion process used in
petroleum refineries. It is widely used to convert the high-boiling
hydrocarbon fractions of petroleum crude oils to more valuable gasoline,
olefinic gases (light olefins) and other product. The FCC feedstock may
comprise a fraction of the crude oil that has an initial boiling point of
340° C. or higher at atmospheric pressure and an average molecular
weight ranging from about 200 to 600 or higher. The FCC process vaporizes
and breaks the long-chain molecules of the high-boiling hydrocarbon
liquids into much shorter molecules by contacting the feedstock, at high
temperature and moderate pressure, with a fluidized powdered catalyst.
Subjecting CC feedstock to catalytic cracking 302 may comprise cracking
the oil feedstock (i.e., the FCC feedstock) in the presence of a finely
divided catalyst, by any means known in the art. The FCC catalyst may be
maintained in an aerated or fluidized state by the oil vapors. The fluid
catalytic cracker may contain a catalyst section and a fractionating
section that operate together as an integrated processing unit. The
catalyst section can contain the reactor and regenerator, which, with the
standpipe and riser, can form the catalyst circulation unit. The fluid
catalyst can be continuously circulated between the FCC reactor and the
regenerator using air, oil vapors, and/or steam as the conveying media.

[0104]In embodiments, FCC is carried out by mixing a preheated hydrocarbon
charge (i.e., the FCC feedstock) with hot, regenerated catalyst as it
enters the riser leading to the FCC reactor. The charge is combined with
a recycle stream within the riser, vaporized, and raised to reactor
temperature (900° to 1,000° F.) by the hot catalyst. As the
mixture travels up the riser, the charge is cracked at 10 to 30 psi. In
embodiments utilizing modern FCC units, all cracking can occur in the
riser. The FCC `reactor` may thus merely serve as a holding vessel for
the cyclones. Cracking continues until the oil vapors are separated from
the catalyst in the reactor cyclones.

[0105]Providing RRG via 300A further comprises separating the CC offgas
from the CC products. In embodiments in which the catalytic cracking is
fluid catalytic cracking, the resultant FCC product stream (cracked
product) may be fractionated into various fractions, including an FCC
offgas fraction which is utilized as the provided RRG. The products of
the fluid catalytic cracker may thus be introduced into an FCC product
fractionating column where it is separated into fractions, including an
FCC offgas fraction.

[0106]Spent FCC catalyst can be regenerated to eliminate coke that
collects on the catalyst during the FCC process. Spent catalyst flows
through the catalyst stripper to the regenerator, where most of the coke
deposits burn off at the bottom where preheated air and spent catalyst
are mixed. Fresh catalyst is added and worn-out catalyst removed to
optimize the cracking process.

[0107]Utilizing FCC offgas for the RRG of the disclosed method may be more
desirable than conventional treatment of such offgas. Conventionally, the
main fractionator offgas is sent to what is called a gas recovery unit
where it is separated into butanes and butylenes, propane and propylene,
and lower molecular weight gases (hydrogen, methane, ethylene and
ethane). Some conventional FCC gas recovery units also separate out some
of the ethane and ethylene.

[0108]Conventionally, olefins recovery from refinery FCC offgas streams
has been used to provide cash flow from olefins from a tail-gas stream
that has typically been consumed as refinery fuel or flared. Such
recovery schemes can be employed in refineries or olefins plants, and can
be tailored to fit individual requirements. However, the conventional
treatment of FCC off-gas is, complex and capital intensive. In
embodiments, as shown in FIG. 4, FCC offgas is further treated, for
example, as shown in FIG. 5, to remove olefins as known in the art and
only the light gas remaining after removal of various products is
utilized as RRG. As shown in FIG. 5, all or a portion of the light C1 to
C4 gases that are taken off the FCC unit and may also contain H2, CO
and/or S, may be used as RRG according to this disclosure.

[0109]In embodiments, subjecting the CC feedstock to catalytic cracking
302 comprises subjecting the CC feedstock to moving bed catalytic
cracking, by methods known in the art. The moving-bed catalytic cracking
process is similar to the FCC process. The catalyst is in the form of
pellets that are moved continuously to the top of the unit by conveyor or
pneumatic lift tubes to a storage hopper, then flow downward by gravity
through the reactor, and finally to a regenerator. The regenerator and
hopper are isolated from the reactor by steam seals. The cracked product
is separated into recycle gas, oil, clarified oil, distillate, naphtha,
and wet gas. The gas or wet gas or a portion thereof may be used as
provided RRG.

[0110]In embodiments, subjecting the CC feedstock to catalytic cracking
302 comprises subjecting the CC feedstock to Thermofor catalytic
cracking, as known in the art. In a typical thermofor catalytic cracking
unit, the preheated feedstock flows by gravity through the catalytic
reactor bed. The vapors are separated from the catalyst and sent to a
fractionating tower, from which CC offgas may be obtained for use as RRG.
The spent catalyst is regenerated, cooled, and recycled. The flue gas
from regeneration is sent to a carbon-monoxide boiler for heat recovery.

[0111]In embodiments, providing RRG comprises recovering offgas (which is
normally sent to the gas plant of a refinery) from thermal cracking.
Thermal cracking is the breaking up of heavy oil molecules into lighter
fractions by the use of high temperature without the aid of catalysts.
Thermal cracking subjects heavy fuels to both pressure and intense heat,
physically breaking the large molecules into smaller ones to produce
additional gasoline and distillate fuels. The thermal cracking utilized
to produce the RRG as offgas may be visbreaking, another form of thermal
cracking.

[0112]Because the simple distillation of crude oil produces amounts and
types of products that are not consistent with those required by the
marketplace, subsequent refinery processes change the product mix by
altering the molecular structure of the hydrocarbons. One of the ways of
accomplishing this change is through `cracking,` a process that breaks or
cracks the heavier, higher boiling-point petroleum fractions into more
valuable products such as gasoline, fuel oil, and gas oils. The two basic
types of cracking are thermal cracking, using heat and pressure, and
catalytic cracking, which is discussed above.

[0113]The RRG may be an offgas (conventionally sent to gas plant, fuel, or
flare) of a thermal cracking process selected from visbreaking, steam
cracking, coking, and combinations thereof.

[0114]The RRG may be obtained via visbreaking Visbreaking is a mild form
(low temperature) of thermal cracking that significantly lowers the
viscosity or pour point of heavy crude-oil residue (straight-run
residuum) without affecting the boiling point range. Residual from an
atmospheric distillation tower may be heated (800° F. to
950° F.) at atmospheric pressure and mildly cracked in a heater.
It may then be quenched with cool gas oil to control overcracking, and
flashed in a distillation tower. Visbreaking is conventionally used to
reduce the pour point of waxy residues and reduce the viscosity of
residues used for blending with lighter fuel oils. Middle distillates may
also be produced via visbreaking, depending on product demand. The
thermally cracked residue tar, which accumulates in the bottom of the
fractionation tower, is vacuum flashed in a stripper and the distillate
recycled. Table 3 indicates typical feedstocks and resulting products of
visbreaking, and indicates the potential use of the offgas of visbreaking
operations or a portion thereof for RRG.

[0115]In embodiments, providing RRG 300 comprises providing pyrolysis gas.
Pyrolysis gas is a by-product from the manufacture of ethylene by steam
cracking of hydrocarbon fractions such as naphtha or gas oil. Pyrolysis
gasoline or pygas may be obtained or produced as a byproduct in a steam
cracking olefin plant and may consist of C5- to C10-hydrocarbons. A
suitable pyrolysis gas production apparatus is indicated in FIG. 6. Pygas
is generally used as a feedstock for the production of aromatics (e.g.
benzene), but is also sometimes applied for other purposes such as
gasoline production. Because the raw pygas contains unstable or undesired
components such as dienes, olefins and sulfur components, the stream is
conventionally subjected to (2-stage) hydrogenation or hydrotreatment.
Hydrotreating also can be employed to improve the quality of pyrolysis
gasoline (pygas), a by-product from the manufacture of ethylene.
Traditionally, the outlet for pygas has been motor gasoline blending, a
suitable route in view of its high octane number. However, only small
portions can be blended untreated owing to the unacceptable odor, color,
and gum-forming tendencies of this material. The quality of pygas, which
is high in diolefin content, is conventionally sometimes improved by
hydrotreating, whereby conversion of diolefins into mono-olefins provides
an acceptable product for motor gas blending. Such hydrotreatment may be
undesirable in light of the method of producing oxygenates presented
herein, which may utilize pygas to produce valuable products.

[0116]According to embodiments of this disclosure, pygas may be utilized
for the production of value-added products. RRG may be provided via the
method of providing RRG 300B presented in the flowchart of FIG. 11.
Providing RRG 300B comprises providing steam cracker feedstock 308,
cracking the steam cracker feedstock to provide cracked products 309, and
separating pyrolysis gas from cracked products 310. Providing steam
cracker feedstock 308 may comprise producing or obtaining any suitable
steam cracker feedstock as known in the art. The steam cracker feedstock
comprises naphtha. Naphtha is a general term used for low boiling
hydrocarbon fractions that are a major component of gasoline. Aliphatic
naphtha refers to those naphthas containing less than 0.1% benzene and
with carbon numbers from C3 through C16. Aromatic naphthas have carbon
numbers from C6 through C16 and contain significant quantities of
aromatic hydrocarbons such as benzene (>0.1%), toluene, and xylene.
Naphtha is used primarily as feedstock for producing a high octane
gasoline component (via the catalytic reforming process). It is also used
in the petrochemical industry for producing olefins in steam crackers and
in the chemical industry for solvent (cleaning) applications.

[0117]The steam cracker feedstock may range from ethane to vacuum gas oil,
with heavier feeds giving higher yields of by-products such as naphtha.
The steam cracker feedstock may comprise ethane, butane, naphtha, or a
combination thereof. Cracking steam cracker feedstock to provide cracked
products 309 comprises introducing the steam cracker feedstock into a
steam cracker, which is a petrochemical apparatus that converts a steam
cracker feedstock (e.g. naphtha and perhaps light hydrocarbons) into
olefins (e.g. ethylene, propylene), and other chemical raw materials. In
embodiments, the steam cracking is carried out at temperatures of
1,500° F. to 1,600° F., and at pressures slightly above
atmospheric. Following cracking of the steam cracker feedstock 309, the
pyrolysis gas is separated from the cracked products at 310. The cracked
products (chemicals) can be processed as conventionally, e.g.
transported, via pipeline and other methods, to petrochemical and polymer
facilities and converted into olefin-based products. Naphtha produced
from steam cracking typically contains benzene, which is extracted prior
to hydrotreating. Residual from steam cracking is sometimes blended into
heavy fuels. The pyrolysis gas may be provided as RRG 300 according to
this disclosure.

[0118]In embodiments, providing RRG 300 comprises producing or obtaining
coker offgas by any method known in the art. An exemplary system for
providing coker offgas is provided in FIG. 7. FIG. 12 is a flow diagram
of a method of producing coker offgas for providing as RRG 300C according
to an embodiment of this disclosure. Providing RRG 300C comprises
providing coker feedstock 311, thermally cracking coker feedstock 312,
and extracting coker offgas from coker products 313. The coker offgas may
be obtained from coking, which is a process for thermally converting and
upgrading heavy residual into lighter products and by-product petroleum
coke. Coke is the high carbon-content residue remaining from the
destructive distillation of petroleum residue.

[0119]Coking is a severe method of thermal cracking used to upgrade heavy
residuals into lighter products or distillates. Providing coker feedstock
311 may comprise providing residual from an atmospheric tower and/or a
vacuum distillation tower. Coking of coker feedstock may produce
straight-run gasoline (coker naphtha) and various middle-distillate
fractions used as catalytic cracking feedstock, along with coker offgas
for use as RRG according to this disclosure. Coking so completely reduces
hydrogen that the residue is a form of carbon called `coke.` Delayed
coking and/or continuous (contact or fluid) coking may provide the coker
offgas for use as RRG.

[0120]In embodiments, RRG is provided as offgas from delayed coking Vacuum
resid is conventionally processed in delayed coking units which convert
heavy oil from crude into lighter products. In delayed coking the heated
charge (coker feedstock, typically residuum from atmospheric distillation
tower) is transferred to large coke drums which provide the long
residence time needed to allow the cracking reactions to proceed to
completion. Initially the heavy feedstock is fed to a furnace which heats
the residuum to high temperatures (900° F. to 950° F.) at
low pressures (25 to 30 psi) and is designed and controlled to prevent
premature coking in the heater tubes. The mixture is passed from the
heater to one or more coker drums where the hot material is held
approximately 24 hours (delayed) at pressures of 25 to 75 psi, until it
cracks into lighter products. Vapors from the drums are returned to a
fractionator where offgas, naphtha, and gas oils are separated. The coker
offgas may be used to provide RRG 300.

[0121]Conventionally, when the coke reaches a predetermined level in one
drum, the flow is diverted to another drum to maintain continuous
operation. The full drum is steamed to strip out uncracked hydrocarbons,
cooled by water injection, and decoked by mechanical or hydraulic
methods. The coke may be mechanically removed by an auger rising from the
bottom of the drum. Hydraulic decoking consists of fracturing the coke
bed with high-pressure water ejected from a rotating cutter.

[0122]In embodiments, RRG is provided as offgas from continuous coking.
Continuous (contact or fluid) coking is a moving-bed process that
operates at temperatures higher than delayed coking. In continuous
coking, thermal cracking occurs by using heat transferred from hot,
recycled coke particles to feedstock in a radial mixer, called a reactor,
at a pressure of 50 psi. Gases and vapors are taken from the reactor,
quenched to stop any further reaction, and fractionated. As indicated in
Table 4 which tabulates typical feedstocks and products of coking
operations, the coker offgas or a portion thereof may be used as RRG
according to this disclosure. The reacted coke enters a surge drum and is
lifted to a feeder and classifier where the larger coke particles are
removed as product. The remaining coke is dropped into the preheater for
recycling with feedstock. Coking occurs both in the reactor and in the
surge drum. The process is automatic in that there is a continuous flow
of coke and feedstock. As mentioned hereinabove, potential off gas
compositions are also described in Petroleum Refinery Distillation second
edition by R. N. Watkins (ISBN 0-87201-672-2).

[0123]In embodiments, providing RRG 300 comprises providing associated
gas. A method of providing associated gas 300D utilizing associated gas
is presented in FIG. 13. Providing RRG 300D comprises providing crude oil
314 and separating associated gas from crude oil 315. Providing crude oil
314 may be performed as with step 304 described above in relation to FIG.
10. Associated gas is gas found dissolved in crude oil at the high
pressures existing in a reservoir, or gas present as a gas cap over the
oil. Associated gas comprises natural gas. Separating associated gas from
crude oil may be performed as known in the art.

[0124]Other refinery-related gas may be used as RRG according to this
disclosure. Any gas conventionally sent to a gas plant can be used as RRG
and converted to value-added product via the method of this disclosure.
For example, offgas produced during hydrodesulfurization or a portion
thereof may be used to provide RRG. Hydrodesulfurization refers to a
catalytic process in which the principal purpose is to remove sulfur from
petroleum fractions in the presence of hydrogen. In embodiments, one or
more product is removed from a gas conventionally sent to a gas treating
plant prior to its use as RRG. Unsaturated and or saturated gas plants
may remove one or more components prior to use of the gas as RRG. For
example, butanes and butenes may be removed for use as alkylation
feedstock, heavier components may be sent to gasoline blending, propane
may be recovered for LPG, and propylene may be removed for use in
petrochemicals.

[0125]Intimately Mixing RRG with Carrier and/or Catalyst to Form
Value-Added Product. The disclosed process for the production of
value-added products from refinery-related gas 250 further comprises
intimately mixing the provided RRG with carrier and/or catalyst to form a
dispersion and value-added product 400. The value-added products may
comprise olefins and/or oxygenates, including alcohols. Incorporating one
or more HSD 40 into a conventional refinery may be especially desirable.
Sulfuric acid may be a most suitable carrier, as sulfuric acid is the
most commonly used acid treating process found in a typical oil refinery.
Additionally, the RRG will typically comprise sulfur, and the high shear
process may convert the sulfur in the RRG to sulfuric acid, which may be
removed with the carrier. Sulfuric acid treatment is a process in which
unfinished petroleum products such as gasoline, kerosene, and lubricating
oil stocks are treated with sulfuric acid to improve color, odor, and
other properties.

[0126]Conventional sulfuric acid treating results in partial or complete
removal of unsaturated hydrocarbons, sulfur, nitrogen, and oxygen
compounds, and resinous and asphaltic compounds. It is used to improve
the odor, color, stability, carbon residue, and other properties of the
oil. A portion of the sulfuric acid at the refinery may be used to
produce value-added product from various RRGs according to this
disclosure.

[0127]Intimately mixing 400 may comprise subjecting a mixture of the RRG
and carrier and/or catalyst to a shear rate of at least 20,000 s-1
or greater, as further discussed hereinbelow. Intimately mixing 400 may
comprise mixing to form a dispersion comprising bubbles of RRG dispersed
in the carrier (which may be or contain catalyst), wherein the bubbles
have an average particle diameter of about 5, 4, 3, 2, 1, or less than 1
micron. In embodiments, the bubbles have an average particle diameter in
the nanometer range, the micron range, or the submicron range.

[0128]Referring now to FIG. 1, intimately mixing 400 may comprise
introducing a suitable RRG via dispersible gas stream 22 and a carrier
and/or catalyst via stream 21 into a high shear device 40. The HSD may be
a rotor-stator device as described hereinabove.

[0129]In operation, a dispersible gas stream comprising RRG is introduced
into system 100 via line 22, and combined in line 13 with a carrier
stream to form a gas-liquid stream. The carrier may be or contain therein
a catalyst. The carrier 21 may be any suitable liquid carrier, and may be
aqueous or organic. In embodiments, the carrier comprises sulfuric acid,
which also acts as a catalyst. In embodiments, the carrier and/or
catalyst is selected from sulfuric acid, phosphoric acid, sulfonic acid,
and combinations thereof. In embodiments, a catalyst suitable for
catalyzing a hydration reaction is employed. An inert gas such as
nitrogen may be used to fill reactor 10 and purge it of any air and/or
oxygen prior to operation of system 100. According to an embodiment, the
catalyst is phosphoric acid disposed on a solid support such as without
limitation, silica. In other embodiments, the catalyst may be sulfuric
acid or sulfonic acid. In embodiments, the catalyst comprises a zeolite.
Examples of the zeolites usable in various embodiments include
crystalline aluminosilicates such as mordenite, erionite, ferrierite and
ZSM zeolites developed by Mobil Oil Corp.; aluminometallosilicates
containing foreign elements such as boron, iron, gallium, titanium,
copper, silver, etc.; and metallosilicates substantially free of
aluminum, such as gallosilicates and borosilicates. As regards the
cationic species which are exchangeable in the zeolites, the
proton-exchanged type (H-type) zeolites are usually used, but it is also
possible to use the zeolites which have been ion-exchanged with at least
one cationic species, for example, an alkaline earth element such as Mg,
Ca and Sr, a rare earth element such as La and Ce, a VIII-group element
such as Fe, Co, Ni, Ru, Pd and Pt, or other element such as Ti, Zr, Hf,
Cr, Mo, W and Th. Catalyst may be fed into reactor 10 through a catalyst
feed stream. Alternatively, catalyst may be present in a fixed or
fluidized bed 10.

[0130]Alternatively, the dispersible gas may be fed directly into HSD 40,
instead of being combined with the carrier (e.g. sulfuric acid) in line
13. Pump 5 is operated to pump the carrier through line 21, and to build
pressure and feed HSD 40, providing a controlled flow throughout high
shear (HSD) 40 and high shear system 100. In some embodiments, pump 5
increases the pressure of the HSD inlet stream in line 13 to greater than
200 kPa (2 atm) or greater than about 300 kPa (3 atmospheres). In this
way, high shear system 100 may combine high shear with pressure to
enhance intimate mixing of reactant(s).

[0131]In a preferred embodiment, dispersible RRG gas may continuously be
fed into the carrier stream 13 to form the high shear feed stream (e.g. a
gas-liquid feed stream). In high shear device 40, carrier and the RRG are
highly dispersed such that nanobubbles and/or microbubbles of RRG are
formed for superior dissolution of RRG into solution. Once dispersed, the
dispersion may exit high shear device 40 at high shear outlet line 19.
Stream 19 may optionally enter vessel 10. Vessel 10 may comprise a
fluidized or fixed bed and be used in lieu of or in addition to a slurry
catalyst process. However, (e.g. in a slurry catalyst embodiment), high
shear outlet stream 19 may directly enter reactor/vessel 10 for further
reaction. The reaction stream may be maintained at the specified reaction
temperature, using cooling coils in the reactor 10 to maintain reaction
temperature. Reaction products (e.g. value-added product which may
comprise olefins, alcohols, and/or other oxygenates) may be withdrawn at
product stream 17. Unreacted/light gas may be removed from vessel 10 via
line 16. Carrier may be recycled via line 20. Vessel 10 may include one
or more separation vessels for the separation of any combination of
value-added products, light gas, carrier liquid, and catalyst.

[0132]Because the RRG will vary depending on the source of the RRG, the
reactions occurring in HSD 40 and/or vessel 10 and the resulting
value-added product will vary. Reactions that may occur are FT reactions
(e.g. when RRG comprises carbon monoxide and hydrogen, i.e., synthesis
gas; FT catalyst may be utilized), olefin hydration reactions (e.g. when
RRG comprises olefins; carrier may comprise sulfuric acid; zeolite
catalyst may be present), methanol production (e.g. when RRG comprises
methane; carrier may comprise sulfuric acid), cracking reactions, and
various other reactions, as known in the art and discernible without
undue reaction, via experimentation with a desired RRG. As mentioned, FT
reactions may occur within system 100. Such reactions are described in
U.S. patent application Ser. No. 12/138,269, which is hereby incorporated
herein in its entirety for all purposes not inconsistent with this
disclosure. Olefin hydration reactions may occur in system 100. Such
reactions are described in U.S. Pat. No. 7,482,497 and U.S. patent
application Ser. Nos. 12/335,270 and 12/140,763, each of which is
incorporated hereby herein in its entirety for all purposes not
inconsistent with this disclosure.

[0133]Value-added product will generally comprise at least one component
selected from oxygenates and olefins. In embodiments, value-added product
comprises at least one alcohol. The alcohol may comprise ethanol,
propanol, isopropanol, butanol, or a combination thereof. High shear
conversion of olefin feedstock to product comprising alcohol is described
in U.S. patent application Ser. No. 12/335,270, which is hereby
incorporated herein in its entirety for all purposes consistent with this
disclosure. Any source of OH can be used to form the alcohol, for example
water may provide the OH source. In embodiments, for example, RRG
comprises FCC offgas. In embodiments, the FCC offgas comprises ethylene
and/or ethane. In such and/or other embodiments, the value-added product
comprises primarily alcohols. In embodiments, the value-added product
comprises at least one selected from oxygenates. In embodiments, the
value-added product comprises at least one selected from alcohols.

[0134]The reactants are intimately mixed within HSD 40, which serves to
subject the reactants to high shear. It is also envisaged that a catalyst
may additionally be present in the reactant stream in certain
embodiments. For example, a solid, gaseous or liquid phase catalyst may
be introduced to HSD 40 via inlet line 13, line 21, or line 22. In an
exemplary embodiment, the high shear device comprises a commercial
disperser such as IKA® model DR 2000/4, a high shear, three stage
dispersing device configured with three rotors in combination with
stators, aligned in series, as described above. The disperser is used to
create the dispersion of RRG in the liquid carrier. The rotor/stator sets
may be configured as illustrated in FIG. 2, for example. In such an
embodiment, the combined reactants enter the high shear device via line
13 and enter a first stage rotor/stator combination having
circumferentially spaced first stage shear openings. The coarse
dispersion exiting the first stage enters the second rotor/stator stage,
which has second stage shear openings. The reduced bubble-size dispersion
emerging from the second stage enters the third stage rotor/stator
combination having third stage shear openings. The rotors and stators of
the generators may have circumferentially spaced complementarily-shaped
rings. The dispersion exits the high shear device via line 19. In some
embodiments, the shear rate increases stepwise longitudinally along the
direction of the flow 260, or going from an inner set of rings of one
generator to an outer set of rings of the same generator. In other
embodiments, the shear rate decreases stepwise longitudinally along the
direction of the flow, 260, or going from an inner set of rings of one
generator to an outer set of rings of the same generator (outward from
axis 200). For example, in some embodiments, the shear rate in the first
rotor/stator stage is greater than the shear rate in subsequent stage(s).
For example, in some embodiments, the shear rate in the first
rotor/stator stage is greater than or less than the shear rate in a
subsequent stage(s). In other embodiments, the shear rate is
substantially constant along the direction of the flow, with the stage or
stages being the same. If HSD 40 includes a PTFE seal, for example, the
seal may be cooled using any suitable technique that is known in the art.
The HSD 40 may comprise a shaft in the center which may be used to
control the temperature within HSD 40. For example, the carrier stream
flowing in line 13 may be used to cool the seal and in so doing be
preheated as desired prior to entering the high shear device. Heat may be
added to HSD 40 (via the shaft or elsewhere, such as external to HSD 40)
to promote reactions, in embodiments.

[0135]The rotor(s) of HSD 40 may be set to rotate at a speed commensurate
with the diameter of the rotor and the desired tip speed. As described
above, the HSD (e.g., colloid mill or toothed rim disperser) has either a
fixed clearance between the stator and rotor or has adjustable clearance.

[0136]HSD 40 serves to intimately mix the RRG and the carrier. In some
embodiments of the process, the transport resistance of the reactants is
reduced by operation of the high shear device such that the velocity of
the one or more reaction (i.e. reaction rate) is increased by greater
than a factor of about 5. In some embodiments, the velocity of the
reaction is increased by at least a factor of 10. In some embodiments,
the velocity is increased by a factor in the range of about 10 to about
100 fold. In some embodiments, HSD 40 delivers at least 300 L/h at a
nominal tip speed of at least 22 m/s (4500 ft/min), 40 m/s (7900 ft/min),
and which may exceed 225 m/s (45,000 ft/min) or greater. The power
consumption may be about 1.5 kW or higher as desired. Although
measurement of instantaneous temperature and pressure at the tip of a
rotating shear unit or revolving element in HSD 40 is difficult, it is
estimated that the localized temperature seen by the intimately mixed
reactants may be in excess of 500° C. and at pressures in excess
of 500 kg/cm2 under high shear conditions.

[0137]The rate of chemical reactions involving liquids, gases and solids
depend on time of contact, temperature, and pressure. In cases where it
is desirable to react two or more raw materials of different phases (e.g.
solid and liquid; liquid and gas; solid, liquid and gas), one of the
limiting factors controlling the rate of reaction involves the contact
time of the reactants. When reaction rates are accelerated, residence
times may be decreased, thereby increasing obtainable throughput.

[0138]In the case of heterogeneously catalyzed reactions there is the
additional rate limiting factor of having the reacted products removed
from the surface of the solid catalyst to permit the catalyst to catalyze
further reactants. Contact time for the reactants and/or catalyst is
often controlled by mixing which provides contact with reactants involved
in a chemical reaction.

[0139]Not to be limited by theory, it is known in emulsion chemistry that
sub-micron particles, or bubbles, dispersed in a liquid undergo movement
primarily through Brownian motion effects. Such sub-micron sized
particles or bubbles may have greater mobility through boundary layers of
solid catalyst particles, thereby facilitating and accelerating the
catalytic reaction through enhanced transport of reactants.

[0140]The high shear results in dispersion of the RRG in micron or
submicron-sized bubbles or droplets. In some embodiments, the resultant
dispersion has an average bubble size less than about 1.5 μm.
Accordingly, the dispersion exiting HSD 40 via line 19 comprises micron
and/or submicron-sized gas bubbles. In some embodiments, the mean bubble
size is in the range of about 0.4 μm to about 1.5 μm. In some
embodiments, the resultant dispersion has an average bubble or droplet
size less than or about 1 μm. In some embodiments, the mean bubble
size is less than about 400 nm, and may be less than or about 100 nm in
some cases. In many embodiments, the microbubble dispersion is able to
remain dispersed at atmospheric pressure for at least 15 minutes.

[0141]Once dispersed, the resulting dispersion exits HSD 40 via line 19
and feeds into vessel 10, as illustrated in FIG. 1. As a result of the
intimate mixing of the reactants prior to entering vessel 10, a
significant portion of the chemical reactions may take place in HSD 40,
with or without the presence of a catalyst. Accordingly, in some
embodiments, reactor/vessel 10 may be used primarily for heating and
separation of volatile reaction products from the value-added product.
Alternatively, or additionally, vessel 10 may serve as a primary reaction
vessel where most of the value-added product is produced. Vessel/reactor
10 may be operated in either continuous or semi-continuous flow mode, or
it may be operated in batch mode. The contents of vessel 10 may be
maintained at a specified reaction temperature using heating and/or
cooling capabilities (e.g., cooling coils) and temperature measurement
instrumentation, employing techniques that are known to those of skill in
the art. Pressure in the vessel may be monitored using suitable pressure
measurement instrumentation, and the level of reactants in the vessel may
be controlled using a level regulator, employing techniques that are
known to those of skill in the art. The contents are stirred continuously
or semi-continuously.

[0142]Conditions of temperature, pressure, space velocity and reactant
composition may be adjusted to produce a desired product profile. The use
of HSD 40 may allow for better interaction and more uniform mixing of the
reactants and may therefore permit an increase in possible throughput
and/or product yield. In some embodiments, the operating conditions of
system 100 comprise a temperature of at or near ambient temperature and
global pressure of at or near atmospheric pressure. Because the HSD 40
provides high pressure (e.g. 150,000 psi) at the tips of the rotors, the
temperature of the reaction may be reduced relative to conventional
reaction systems in the absence of high shear. In embodiments, the
operating temperature is less than about 70% of the conventional
operating temperature, or less than about 60% of the conventional
operating temperature, or less than about 50% of the conventional
operating temperature for the same reaction(s)

[0143]The residence time within HSD 40 is typically low. For example, the
residence time can be in the millisecond range, can be about 10, 20, 30,
40, 50, 60, 70, 80, 90 or about 100 milliseconds, can be about 100, 200,
300, 400, 500, 600, 700, 800, or about 900 milliseconds, can be in the
range of seconds, or can be any range thereamong.

[0144]Commonly known hydration reaction conditions may suitably be
employed as the conditions to promote production of an alcohol by
hydrating olefins in RRG by using catalysts. There is no particular
restriction as to the reaction conditions. The hydration reaction of an
olefin is an equilibrium reaction to the reverse reaction, that is, the
dehydration reaction of an alcohol, and a low temperature and a high
pressure are ordinarily advantageous for the formation of an alcohol.
However, preferred conditions greatly differ according to the particular
starting olefin. From the viewpoint of the rate of reaction, a higher
temperature is preferred. Accordingly, it is difficult to simply define
the reaction conditions. However, in embodiments, a reaction temperature
may range from about 50° C. to about 350° C., preferably
from about 100° C. to about 300° C. Furthermore, the
reaction pressure may range from about 1 to 300 atmospheres,
alternatively 1 to 250 atmospheres.

[0145]If a catalyst is used to promote the reactions, it may be introduced
directly into vessel 10, as an aqueous or nonaqueous slurry or stream.
Alternatively, or additionally, catalyst may be added elsewhere in system
100. For example, catalyst slurry may be injected into line 21. In some
embodiments, line 21 may contain a flowing fresh carrier stream and/or a
recycle stream from vessel 10.

[0146]The bulk or global operating temperature of the reactants is
desirably maintained below their flash points. In some embodiments, the
operating conditions of system 100 comprise a temperature in the range of
from about 50° C. to about 300° C. In specific embodiments,
the reaction temperature in vessel 10, in particular, is in the range of
from about 90° C. to about 220° C. In some embodiments, the
reaction pressure in vessel 10 is in the range of from about 5 atm to
about 50 atm.

[0147]The dispersion may be further processed prior to entering vessel 10,
if desired. In vessel 10, reactions (e.g. olefin hydration) continue. The
contents of the vessel are stirred continuously or semi-continuously, the
temperature of the reactants is controlled (e.g., using a heat
exchanger), and the fluid level inside vessel 10 is regulated using
standard techniques. Reaction may occur either continuously,
semi-continuously or batch wise, as desired for a particular application.

[0148]Separating Light Gas, Carrier, Catalyst and Value-Added Product(s).
Method 250 further comprises separating light gas, carrier and
value-added product 500. In instances where the carrier is not the
catalyst or another catalyst (e.g., solid catalyst) is utilized, 500 may
further comprise separating the solid catalyst from the other components
in vessel 10. This separation may be performed via vessel 10 or via
separate separation vessels. Any light reaction gas that is produced or
unreacted components of RRG may exit reactor 10 via gas line 16. In
embodiments, this gas stream is recycled to HSD 40. Any suitable
separation method known in the art may be used to separate the light gas,
carrier liquid, catalyst (if present), and value-added products. For
example, one or more of vapor liquid separations, solid/liquid
separations, distillations, and other separation means may be used to
separate the desired components exiting HSD 40 and/or vessel 10.

[0149]Subjecting Light Gas to High Shear. Method 250 may further comprise
subjecting light gas to high shear 600. The light gas 16 may comprise
carbon dioxide, hydrogen, methane, and various other light components. In
embodiments, subjecting light gas 16 to high shear 600 comprises
intimately mixing light gas in the presence of FT catalyst, whereby FT
product is produced. In this manner, gas-to-liquids production of FT
liquid hydrocarbons may be effected. Any suitable FT catalyst may be
utilized. The high shear FT process may be carried out as described in
U.S. patent Ser. No. 12/138,269. In such embodiments, a portion of the
HSD may be made from or coated with FT catalyst, slurry of FT catalyst
may be circulated, or vessel 10 may comprise a fixed or slurry bed of FT
catalyst. Liquid hydrocarbons may be extracted from vessel 10.

[0150]Subjecting light gas to high shear, 600 may comprise intimately
mixing the crude oil and the light gas. In an embodiment, as shown in
FIG. 14, the gas in line 16 is utilized in a method 600A of stabilizing
and/or altering the API gravity of crude oil, as indicated in FIG. 14.
This method comprises providing crude oil and gas selected from
associated gas, unassociated gas, light gas from step 600 of FIG. 1, RRG,
oxygenates and combinations thereof 601 and subjecting the crude oil and
the selected gas to high shear 602. RRG may be obtained as described in
relation to FIGS. 9-13. Associated gas may be obtained as described in
relation to FIG. 13. The phrase `unassociated gas` herein refers to gas
obtained in a reservoir in the absence of oil, as known in the art. The
crude oil may be provided as described with respect to step 304 in FIG.
10 and step 314 in FIG. 13 hereinabove. The crude oil and selected gas
may be subjected to high shear by introduction into a HSD 40, as
discussed hereinabove. In embodiments, crude oil extracted from the earth
with associated gas is intimately mixed via HSD 40 (desirably before
pressure reduction) to adjust the stability and/or the API gravity
thereof. In embodiments, crude oil extracted from the earth (with or
without associated gas) is intimately mixed with unassociated gas via HSD
40 to adjust the stability/API gravity thereof. Intimately mixing the
crude oil with the selected gas may comprise running the crude oil
through one or more HSDs 40. Intimately mixing the crude oil with the
selected gas may comprise running the crude oil through two or more HSDs
40. Intimately mixing the crude oil with the selected gas may comprise
running the crude oil through three or more HSDs 40. Additional selected
gas may be introduced into each subsequent HSD. Method 600A may be
utilized to alter the API gravity and/or stabilize the crude oil, by
reducing volatile components therein. In embodiments, the API is
increased by a factor of at least or about 1.5 or 2 by the method of
600A. In embodiments, the API of a crude oil is increased from about 15
to about 30, from about 5 to about 20, or from about 10 to about 20 via
method 600A. Method 600A may be utilized to reduce the production of
undesirable asphaltenes during refinery operations. The term
`asphaltenes` refers to the asphalt compounds soluble in carbon disulfide
but insoluble in paraffin naphthas.

[0151]The value-added product recovered via line 17 may be further treated
as known in the art. For example, value-added product may be contacted
with cold water to remove sulfuric acid therefrom. The products, for
example oxygenates, may be used and/or separated as known in the art.
Separated components may be recycled, as desired.

[0152]Carbon Dioxide Reduction. In an embodiment, carbon dioxide
(considered as a RRG gas and a greenhouse gas) and water are converted to
a value-added product. In some embodiments, the value added-product
comprises alcohols such as methanol. In some other embodiments, the value
added-product comprises aldehydes and ketones and other organic
oxygenates.

[0153]In some embodiments, the carbon dioxide source is a Refinery-Related
Gas (RRG) from a power plant, which includes mainly N2, CO2,
water, some O2, CO, sulfur, and nitrous oxides. In petroleum
refining embodiments, where there is little unsaturation, sulfur, and/or
oxygen, hydrogen is present. In some embodiments, the carbon dioxide
source is a blast furnace gas. In some cases, the main composition of the
blast furnace gas is 46% nitrogen, 24% carbon monoxide, 26% carbon
dioxide, 4% hydrogen, some amount of oxygen and methane. In some
embodiments, the carbon dioxide source is a FCC off-gas. In some cases,
the main composition of the FCC off-gas is 1.1% H2, 13.31% N2,
1.54% CO, 27.48% CH4, 22.94% C2H4, 23.35% C2H6,
2.11% C3H6, 0.4% C3H8, 4.61% C4H8, 0.27%
C4H10, and 2.63% C5+.

[0154]In some embodiments, the carbon dioxide comes from a fossil fuel
(e.g., coal, natural gas, petroleum) burning facility (FFBF) or some
components thereof. In some cases, the fossil fuel burning facility
(FFBF) is a power plant or a power station. In some other cases, the FFBF
is a burner or furnace. Such FFBF's are known to one skilled in the art.
This disclosure does not intend to differentiate the FFBF by its size,
purpose of function, or mechanism of operation.

[0155]In some embodiments, the conversion of carbon dioxide and water is
promoted by a bio-catalytic substance (e.g., an enzyme). In some
embodiments, the reaction is promoted by electro catalytic methods. In
some cases, carbon dioxide and water are converted to methanol.

[0156]In some embodiments, the conversion of carbon dioxide and water is
promoted by a bio-catalytic substance (e.g., an enzyme) in conjunction
with an inorganic catalyst as described hereinabove. In some cases,
carbon dioxide and water are converted to alcohols, aldehydes and ketones
and other organic oxygenates.

[0157]Without wishing to be limited by theory, it is contemplated that the
reaction between carbon dioxide and water is accelerated through the
creation of free radicals from H2O and CO2 under high shear
conditions. Furthermore, the intimated mixing and cavitation effects
caused by high shear reduce mass transfer limitations so that the
reaction rate is increased.

[0158]Various dimensions, sizes, quantities, volumes, rates, and other
numerical parameters and numbers have been used for purposes of
illustration and exemplification of the principles of the invention, and
are not intended to limit the invention to the numerical parameters and
numbers illustrated, described or otherwise stated herein. Likewise,
unless specifically stated, the order of steps is not considered
critical. The different teachings of the embodiments discussed below may
be employed separately or in any suitable combination to produce desired
results.

[0159]Multiple Pass Operation. In the embodiment shown in FIG. 1, the
system is configured for single pass operation, wherein the product
produced in HSD 40 continues along flow line 17. The output of HSD 40 may
be run through a subsequent HSD. In some embodiments, it may be desirable
to pass the contents of flow line 19, or a fraction thereof, through HSD
40 during a second pass. In this case, at least a portion of the contents
of flow line 19 may be recycled from flow line 19 and pumped by pump 5
into line 13 and thence into HSD 40. Additional reactants may be injected
via line 22 into line 13, or may be added directly into the HSD. In other
embodiments, product is further treated prior to recycle of a portion
thereof to HSD 40.

[0160]Multiple HSDs. In some embodiments, two or more HSDs like HSD 40, or
configured differently, are aligned in series, and are used to promote
further reaction. Operation of the mixers may be in either batch or
continuous mode. In some instances in which a single pass or "once
through" process is desired, the use of multiple HSDs in series may also
be advantageous. In embodiments, the reactants pass through multiple HSDs
40 in serial or parallel flow. For example, in embodiments, product in
outlet line 19 is fed into a second HSD. When multiple HSDs 40 are
operated in series or in parallel, additional reactants and/or carrier
(liquid or gaseous) may be injected into the inlet feedstream of each
HSD. For example, different dispersible gas, such as hydrogen, carbon
dioxide, and/or carbon monoxide may be introduced into a second or
subsequent HSD 40. In embodiments, gas comprising oxygenate is injected
into the inlet feedstream. For example, gas comprising carbon monoxide,
carbon dioxide, oxygen, light alcohols, or a combination thereof may be
introduced into the inlet of each in a series or parallel arrangement of
HSDs.

[0161]For example, a first HSD 40 may be used to convert RRG comprising
FCC offgas comprising ethylene and/or ethane to product comprising
ethanol and/or other oxygenate(s) and/or higher hydrocarbons. Gas
remaining or produced within HSD 40 exits vessel 10 via light product gas
outlet line 16. Gas in light product outlet line 16 may be recycled to
HSD 40 or introduced into a second HSD along with liquid carrier. The
light gas in light gas outlet line 16 may comprise hydrogen, for example.
The light gas in light gas outlet line 16 may be introduced into the
serial HSD along with additional gas, for example, another available RRG.
The additional gas may comprise, for example, carbon dioxide, carbon
monoxide, methane, or a combination thereof. For example, carbon monoxide
and/or carbon dioxide may be available from regeneration of FCC catalyst.
The same or a different catalyst may be used in HSD 40 and a second or
subsequent HSD. The catalyst may be selected based upon the gas to be
treated therein. In some embodiments, multiple HSDs 40 are operated in
parallel, and the outlet products therefrom are introduced into one or
more flow lines 19. Any gas remaining following treatment via the
disclosed method may be utilized as fuel or flared. This amount will
generally be much less than the amount of gas conventionally used for
fuel or flare in a typical refinery.

[0162]Features. The intimate contacting of reactants within HSD 40 may
result in faster and/or more complete reaction of reactants. In
embodiments, use of the disclosed process comprising reactant mixing via
external HSD 40 allows use of reduced quantities of catalyst than
conventional configurations and methods and/or increases the product
yield and/or the conversion of reactants. In embodiments, the method
comprises incorporating external HSD 40 into an established process
thereby reducing the amount of catalyst required to effect desired
reaction(s) and/or enabling an increase in production throughput from a
process operated without HSD 40, for example, by reducing downtime
involved in replacement of catalyst in a conventional slurry bed reactor.
In embodiments, the disclosed method reduces operating costs and/or
increases production from an existing process. Alternatively, the
disclosed method may reduce capital costs for the design of new
processes.

[0163]Without wishing to be limited to a particular theory, it is believed
that the level or degree of high shear mixing may be sufficient to
increase rates of mass transfer and also produce localized non-ideal
conditions (in terms of thermodynamics) that enable reactions to occur
that would not otherwise be expected to occur based on Gibbs free energy
predictions. Localized non ideal conditions are believed to occur within
the HSD resulting in increased temperatures and pressures with the most
significant increase believed to be in localized pressures. The increases
in pressure and temperature within the HSD are instantaneous and
localized and quickly revert back to bulk or average system conditions
once exiting the HSD. Without wishing to be limited by theory, in some
cases, the HSD may induce cavitation of sufficient intensity to
dissociate one or more of the reactants into free radicals, which may
intensify a chemical reaction or allow a reaction to take place at less
stringent conditions than might otherwise be required. Cavitation may
also increase rates of transport processes by producing local turbulence
and liquid micro-circulation (acoustic streaming). An overview of the
application of cavitation phenomenon in chemical/physical processing
applications is provided by Gogate et al., "Cavitation: A technology on
the horizon," Current Science 91 (No. 1): 35-46 (2006). The HSD of
certain embodiments of the present system and methods may induce
cavitation whereby one or more reactant is dissociated into free
radicals, which then react. In embodiments, the extreme pressure at the
tips of the rotors/stators leads to liquid phase reaction, and no
cavitation is involved.

EXAMPLES

[0164]The following section provides further details regarding examples of
various embodiments.

[0165]CO2 and crude are passed through a high shear unit and water
and CO2 are used to create alcohol (high shear: 1000 rpm; reactor
with CO2 at 90° C. and 100 psig).

[0166]Possible mechanism: CO2 reacts with the ruthenium carbonyl to
produce a ruthenium oxide, which then catalyzes the reaction of CO with
water to produce the hydrogen and more carbon dioxide. Hydrogen may then
react with carbon monoxide to produce methanol (CO+2H2=CH3OH),
which is possibly catalyzed by the produced Ruthenium oxide.

[0167]The analysis of the aqueous phase of the sample by Gas
Chromatography (GC) reveals that the aqueous phase of the sample contains
approximately 65% methanol.

[0170]While preferred embodiments of the invention have been shown and
described, modifications thereof can be made by one skilled in the art
without departing from the spirit and teachings of the invention. The
embodiments described herein are exemplary only, and are not intended to
be limiting. Many variations and modifications of the invention disclosed
herein are possible and are within the scope of the invention. Where
numerical ranges or limitations are expressly stated, such express ranges
or limitations should be understood to include iterative ranges or
limitations of like magnitude falling within the expressly stated ranges
or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.;
greater than 0.10 includes 0.11, 0.12, 0.13, and so forth). Use of the
term "optionally" with respect to any element of a claim is intended to
mean that the subject element is required, or alternatively, is not
required. Both alternatives are intended to be within the scope of the
claim. Use of broader terms such as comprises, includes, having, etc.
should be understood to provide support for narrower terms such as
consisting of, consisting essentially of, comprised substantially of, and
the like.

[0171]Accordingly, the scope of protection is not limited by the
description set out above but is only limited by the claims which follow,
that scope including all equivalents of the subject matter of the claims.
Each and every claim is incorporated into the specification as an
embodiment of the present invention. Thus, the claims are a further
description and are an addition to the preferred embodiments of the
present invention. The disclosures of all patents, patent applications,
and publications cited herein are hereby incorporated by reference, to
the extent they provide exemplary, procedural or other details
supplementary to those set forth herein.